EP3194164B1 - Packaging laminate, method for producing same, and packaging container produced from the packaging laminate - Google Patents
Packaging laminate, method for producing same, and packaging container produced from the packaging laminate Download PDFInfo
- Publication number
- EP3194164B1 EP3194164B1 EP15756580.5A EP15756580A EP3194164B1 EP 3194164 B1 EP3194164 B1 EP 3194164B1 EP 15756580 A EP15756580 A EP 15756580A EP 3194164 B1 EP3194164 B1 EP 3194164B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- packaging laminate
- adhesive
- packaging
- adhesive polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004806 packaging method and process Methods 0.000 title claims description 162
- 238000004519 manufacturing process Methods 0.000 title description 10
- 239000010410 layer Substances 0.000 claims description 226
- 229920001684 low density polyethylene Polymers 0.000 claims description 103
- 239000004702 low-density polyethylene Substances 0.000 claims description 103
- 239000002998 adhesive polymer Substances 0.000 claims description 98
- 239000000463 material Substances 0.000 claims description 94
- 229920000642 polymer Polymers 0.000 claims description 79
- 239000011087 paperboard Substances 0.000 claims description 67
- 238000010030 laminating Methods 0.000 claims description 63
- 230000004888 barrier function Effects 0.000 claims description 56
- 238000001125 extrusion Methods 0.000 claims description 56
- 239000000123 paper Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 43
- 239000012790 adhesive layer Substances 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 30
- -1 polyethylene Polymers 0.000 claims description 29
- 239000004698 Polyethylene Substances 0.000 claims description 25
- 229920000573 polyethylene Polymers 0.000 claims description 25
- 238000003475 lamination Methods 0.000 claims description 24
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 claims description 24
- 239000000853 adhesive Substances 0.000 claims description 22
- 230000001070 adhesive effect Effects 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229920001866 very low density polyethylene Polymers 0.000 claims description 22
- 229920001903 high density polyethylene Polymers 0.000 claims description 19
- 239000004700 high-density polyethylene Substances 0.000 claims description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 229920001179 medium density polyethylene Polymers 0.000 claims description 15
- 239000004701 medium-density polyethylene Substances 0.000 claims description 15
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 14
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims description 14
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 14
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 13
- 235000013336 milk Nutrition 0.000 claims description 13
- 239000008267 milk Substances 0.000 claims description 13
- 210000004080 milk Anatomy 0.000 claims description 13
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 11
- 235000013305 food Nutrition 0.000 claims description 11
- 235000021056 liquid food Nutrition 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 11
- 238000011282 treatment Methods 0.000 claims description 9
- 239000008162 cooking oil Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 235000014101 wine Nutrition 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 7
- 238000004381 surface treatment Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 3
- 239000012968 metallocene catalyst Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical group 0.000 claims 3
- 239000005030 aluminium foil Substances 0.000 description 29
- 238000007789 sealing Methods 0.000 description 28
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 16
- 238000000576 coating method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 125000002843 carboxylic acid group Chemical group 0.000 description 12
- 238000007765 extrusion coating Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000005022 packaging material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- PZRHRDRVRGEVNW-UHFFFAOYSA-N milrinone Chemical compound N1C(=O)C(C#N)=CC(C=2C=CN=CC=2)=C1C PZRHRDRVRGEVNW-UHFFFAOYSA-N 0.000 description 6
- 229960003574 milrinone Drugs 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000036541 health Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002775 capsule Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229940044600 maleic anhydride Drugs 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- FAIIFDPAEUKBEP-UHFFFAOYSA-N Nilvadipine Chemical compound COC(=O)C1=C(C#N)NC(C)=C(C(=O)OC(C)C)C1C1=CC=CC([N+]([O-])=O)=C1 FAIIFDPAEUKBEP-UHFFFAOYSA-N 0.000 description 3
- 229920003298 Nucrel® Polymers 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920006113 non-polar polymer Polymers 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001688 coating polymer Polymers 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000021057 semi-liquid food Nutrition 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D85/00—Containers, packaging elements or packages, specially adapted for particular articles or materials
- B65D85/70—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for
- B65D85/72—Containers, packaging elements or packages, specially adapted for particular articles or materials for materials not otherwise provided for for edible or potable liquids, semiliquids, or plastic or pasty materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/62—Boxes, cartons, cases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Definitions
- the present invention relates to a packaging laminate for a packaging container for oxygen-sensitive liquid or semi-liquid food, which packaging laminate comprises a layer of paper or paperboard, and a layer serving as a gas or vapour barrier layer, which layers are bonded to each other by a laminating material, comprising a first adhesive polymer composition in direct contact with the paper or paperboard, the first adhesive polymer composition comprising a polymer material having ethylene monomer units and some monomer units having carboxylic acid functional groups.
- the invention also relates to a packaging container for liquid or semi-food, which packaging container has been produced by folding and sealing the packaging laminate.
- the invention relates to a method of manufacturing such a packaging laminate.
- a known packaging laminate of the type described above generally has a layer of paper or paperboard and outer liquid-tight coatings of polyethylene (PE), preferably low-density polyethylene (LDPE).
- PE polyethylene
- LDPE low-density polyethylene
- the packaging laminate additionally has at least one further layer of a material which provides such barrier properties and which is bonded to the paper or paperboard layer by a lamination layer, preferably low-density polyethylene (LDPE).
- LDPE low-density polyethylene
- Examples of materials for a further layer of this kind can be a layer or film containing a polymer with inherent barrier properties, for example a copolymer of ethylene and vinyl alcohol (EVOH) or a polyamide (PA), or a prefabricated film coated with a liquid-film-coated or vacuum-deposited or vapour-deposited layer having corresponding barrier properties mainly against gases but also against flavouring agents and water vapour.
- a polymer with inherent barrier properties for example a copolymer of ethylene and vinyl alcohol (EVOH) or a polyamide (PA), or a prefabricated film coated with a liquid-film-coated or vacuum-deposited or vapour-deposited layer having corresponding barrier properties mainly against gases but also against flavouring agents and water vapour.
- a common example of coated prefabricated films of this kind is that of oriented films of polyester, for example polyethylene terephthalate (PET) or polypropylene (PP), with a metallized layer or a layer coated by plasma-assisted vapour deposition.
- An aluminium foil is generally used which, in addition to having excellent barrier properties against gases, in particular oxygen, also has the advantageous property of allowing the packaging laminate to be heat-sealed by induction sealing, which is a rapid, simple and effective heat-sealing technique.
- the known packaging laminate is conventionally produced from a web of paper or paperboard which is unwound from a storage reel, while at the same time a web of aluminium is unwound from a corresponding storage reel.
- the two unwound webs are brought together with each other and are both guided through the nip between two adjacent rotatable cylinders, while at the same time a laminating material, usually low-density polyethylene (LDPE), is applied between the webs in order to permanently bind the aluminium web to the paper or paperboard web.
- LDPE low-density polyethylene
- the paper or paperboard web is thereafter provided on both sides with liquid-tight coatings of polyethylene, normally low-density polyethylene (LDPE), and is then wound up on finished packaging reels for onward transport and handling.
- LDPE low-density polyethylene
- Dimensionally stable packaging containers of the single-use type are produced from the packaging laminate with the aid of highly efficient packaging machines of the type that shape, fill and seal finished packages from a web or from prefabricated blanks of the packaging laminate.
- packaging containers are produced by a process in which the web is firstly shaped into a tube by means of both lengthwise edges of the web being joined permanently to each other in an overlap seam by melting together the mutually facing plastic layers of the web.
- the tube is filled with the food product in question, e.g. milk or juice, and is divided into contiguous pillow-shaped packaging units by repeated pressing-together and heat-sealing of the tube transversely with respect to the longitudinal direction of the tube, below the product level of the tube.
- the pillow-shaped packaging units are separated from each other, by cuts made in the transverse sealing zones, and are finally given the desired geometric shape, usually a shape like a brick, by means of at least one further forming and heat-sealing operation.
- a packaging laminate of the known type permits the production of dimensionally stable packaging containers that are product-compatible and consumer-friendly and hold oxygen-sensitive liquid food, for example milk, juice, wine and cooking oil, but are nonetheless associated with disadvantages in terms of both the environment and also processing technology.
- the low-density polyethylene (LDPE) used to bind the aluminium foil to the paper or paperboard layer is a non-polar polymer which in itself lacks natural binding sites for binding to corresponding binding sites on the surface of the aluminium foil. Therefore, in the known method, functional binding sites have to be created synthetically.
- LDPE low-density polyethylene
- a higher temperature in this case at ca 330°C
- ozone is added in order to initiate an oxidation reaction and form polar groups, including free carboxylic acid groups, via which the low-density polyethylene (LDPE) can bind to active binding sites on the surface of the aluminium foil.
- An extrusion at elevated temperature (ca 330°C) entails increased consumption of energy and, consequently, an increased emission of environmentally harmful greenhouse gases ("carbon footprint").
- LDPE low-density polyethylene
- elevated temperature ca 330°C
- these degradation reactions can proceed to such an extent that the desired ability of the polymer to maintain a permanent binding strength between the aluminium foil and the paper or paperboard layer is lost, and the mechanical strength is thereby also lost.
- Ozone which is generally used as an agent for promoting oxidation and adherence, is itself a gas that is harmful to health and to environment, and it has to be handled with the utmost care in order to prevent the gas leaking out. Furthermore, the treatment of the polymer material surface may also lead to degradation reactions and low-molecular degradation products, why it is advantageous if such treatments and chemicals can be avoided in the lamination processes.
- EP 1 118 459 A1 discloses a packaging laminate having the layer sequence paper/adhesive/AI/PET.
- the adhesive is an ethylene-maleic anhydride copolymer with maleic anhydride content of 1.5 wt% (0.4 mol%).
- pre-cut holes in the paperboard which are later laminated over by the various polymer and barrier layers of the laminate, requires close to perfect adhesion between the layers within the laminate membrane area of the pre-cut holes, in order to avoid problems of possible air inclusions, ruptures, leakages problems and penetration of gas molecules into the product. Any occurrence of bad adhesion between the laminated layers, may thus be detrimental to the sterility and integrity of the package, i.e. the ability to resist penetration of gases, micro-organisms and other substances which may harm the packaged food product on the one hand, and the ability to keep tight around the packaged liquid product, not to leak out, on the other hand.
- Another object is to provide a packaging laminate for a packaging container for oxygen-sensitive liquid food, of the type produced by folding and heat-sealing of the packaging laminate, which provides good packaging container integrity according to the above and to provide such packaging containers.
- a further object is to make available a method for producing the packaging laminate, which method can be carried out without unnecessarily excessive consumption of energy, and without the use of substances that are harmful to health and to the environment, in order to achieve and maintain a permanent functional binding between the gas barrier layer and the paper or paperboard layer of the packaging laminate.
- the invention thus provides a packaging laminate for a packaging container for oxygen-sensitive liquid food, such as milk, juice, wine and cooking oil, which packaging laminate comprises a layer of paper or paperboard, and a layer which serves as gas barrier and is bonded to the paper or paperboard layer by a laminating material.
- the packaging laminate thus comprises a layer of paper or paperboard, and a layer of aluminium serving as a gas or vapour barrier layer, which layers are bonded to each other by a laminating material, comprising a central polymer layer which, on one surface, has a first adhesive layer of a first adhesive polymer composition with the ability to bind to the paper or paperboard layer and, on its other surface, has a second adhesive layer of a second adhesive polymer composition with the ability to bind to the layer of aluminium serving as gas barrier, wherein the first adhesive layer on one surface of the central polymer layer is in contact with the paper or paperboard layer, and wherein the second adhesive layer on the other surface of the central polymer layer is in contact with the layer of aluminium serving as gas or vapour barrier, the first adhesive polymer composition comprising ethylene monomer units and from 0,15 to below 1,5 mol%, of monomer units having carboxylic acid functional groups, of the total first adhesive polymer composition, and the second adhesive layer having the same adhesive polymer composition as the first adhesive layer.
- the amount of monomer units having carboxylic acid functional groups in the laminating material is from 0,15 to 1,3 mol%, such as from 0,3 to 0,7 mol%, such as from 0,15 to 0,4 mol%, of the total first adhesive polymer composition.
- relatively high temperatures of the coating polymer melt are required.
- the risk for gel-forming due to polymer degradation in the heated melting and extrusion equipment increases, as well as the formation of soot particles and degradation products in the extruded polymer layer.
- the first adhesive polymer composition further comprises a low density polyethylene (LDPE).
- LDPE low density polyethylene
- Adhesive copolymers from ethylene and (meth)acrylic acid monomer units, having a higher carboxylic group content may be further diluted in a blend composition with LDPE, such that the right amount of carboxylic groups may be obtained for optimal bonding and melt processing properties.
- the composition comprises at least 40 weight percent of the adhesive polymer.
- the first adhesive polymer composition comprises an adhesive polymer selected from the group consisting of ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA) and blends thereof.
- EAA ethylene-acrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- the composition comprises at least 40 weight percent of the EAA and/or EMAA.
- Suitable such adhesive copolymers are found for example with the tradenames of Primacor, Nucrel or Escor.
- the first adhesive polymer composition comprises a low density polyethylene (LDPE) at an amount of up to 60 wt-%.
- LDPE low density polyethylene
- the material layer serving as a barrier layer is aluminium.
- the barrier material is an aluminium foil, but it can also be a metallised polymer film, wherein gas and/or vapour barrier properties are at least partly contributed to the packaging laminate by the metallised layer.
- the material layer serving as a barrier layer is, on its opposite side, which is to form the inside of the packaging laminate in a packaging container, bonded to a heat sealable food product contact layer of polyethylene by an inside adhesive polymer, which is in direct contact with the barrier layer, the inside adhesive polymer consisting of a polymer having ethylene monomer units and monomer units having carboxylic acid functional groups, which amount to from 1,5 mol% and above, preferably from 1,5 mol% to 3,5 mol%, more preferably from 1,5 mol% to 3,3 mol%, of the inside adhesive polymer.
- the inside adhesive polymer is an ethylene acrylic acid copolymer (EAA).
- the higher levels of carboxylic acid functionality in the adhesive polymer bonding to the aluminium foil on the inside, compared to the adhesive polymer bonding to the paper or paperboard layer, are required in the case of packaging of liquid milk and juice.
- free fatty acids that may migrate from the packaged product into and through the inside heat sealable layers towards the aluminium foil barrier, where they are accumulated to high concentrations and acting detrimentally on the adhesion between the aluminium foil and the adjacent inside polymer layer.
- a higher carboxylic acid functionality in this adjacent inside adhesive polymer layer delays the deterioration of the adhesion to the aluminium foil further, thus extending the shelf life of the filled juice package.
- the inside heat sealable polyolefin layers need to be extruded at a lower temperature in order to avoid off-taste generation in the filled milk product due to migrating low-molecular degradation products into the milk.
- a carboxylic acid functional adhesive to be adjacent to the Alfoil, sufficient adhesion of the inside layers to the Alfoil as well as to the innermost heat sealable polyolefin layer is obtainable, although the extrusion temperature may need to be kept rather low.
- the heat sealable food product contact layer comprises or consists of a polyethylene selected from the group consisting of LDPE, linear low density polyethylene (LLDPE) and linear low density polyethylene polymerised by a single site catalyst (m-LLDPE), and blends of two or more thereof.
- the laminating material comprises a central polymer layer which, on one surface, has a first adhesive layer of a first adhesive polymer with the ability to bind to the paper or paperboard layer and, on its other surface, has a second adhesive layer of a second adhesive polymer with the ability to bind to the layer serving as gas barrier, wherein the first adhesive layer on one surface of the central polymer layer is in contact with the paper or paperboard layer, and wherein the second adhesive layer on the other surface of the central polymer layer is in contact with the layer of aluminium serving as gas or vapour barrier, the first adhesive polymer comprising ethylene monomer units and monomer units having carboxylic acid functional groups, which amount to from 0,15 to below 1,5 mol%, preferably from 0,15 to 1,3 mol%, more preferably from 0,15 to 0,7 mol%, most preferably from 0,15 to 0,4 mol%, of the first adhesive polymer, the second adhesive polymer layer having the same adhesive polymer composition as the first adhesive polymer layer.
- the first adhesive polymer comprises an adhesive polymer selected from the group consisting of ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA) and blends thereof.
- EAA ethylene-acrylic acid copolymer
- EMA ethylene-methacrylic acid copolymer
- EAA ethylene-acrylic acid copolymer
- EMA ethylene-methacrylic acid copolymer
- the central polymer layer comprises a non-polar polymer material, such as a polyolefin.
- the first and second adhesive layers of the lamination material can be made from adhesive polymers of different layer thicknesses, but they are preferably made from one and the same adhesive polymer with one and the same layer thickness.
- the first adhesive polymer of the first adhesive layer may be a copolymer having ethylene monomer units and monomer units having carboxylic acid functional groups at an amount of from 0,15 to 1,5 mol%, such as from 0,15 to 1,3 mol%, such as from 0,15 to 0,7 mol%, of the first adhesive polymer.
- the second layer of a second adhesive polymer thus has the same composition as the first adhesive polymer.
- the advantage is not only that a simpler extrusion equipment may be used, by handling only one adhesive polymer melt for supplying the two adhesive layers of the laminate material, but also that gelling problems in the melt extrusion operation of the laminate material layers may be avoided while still achieving good adhesion between all layers concerned.
- the central polymer layer in the laminating material comprises a polyethylene.
- the properties of the central layer can be varied and tailored to achieve various final properties in a packaging laminate.
- linear polymers that can help to improve the mechanical properties of the finished packaging laminate, when they are included in a laminating layer, are so-called linear polymers, for example polyolefins, such as polyethylenes, for example high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and polypropylene (PP).
- polyethylenes for example high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts or with so-called single-
- VLDPE Very low density polyethylene
- ULDPE ultra low density polyethylene
- VLDPE Very low density polyethylene
- ULDPE ultra low density polyethylene
- Linear polymers are understood as polymers which have a more linear molecular structure than LDPE, i.e. which have fewer long-chain branches. Depending on the type and quantity of comonomer, these polymers generally have greater durability in several respects.
- the laminating material and the adhesive polymer it is possible, according to the invention, for the laminating material and the adhesive polymer to be combined and varied within the context of suitable processing properties in extrusion coating and extrusion lamination.
- polyethylenes of the types MDPE, LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) and m-LLDPE While HDPE generally gives, for example, improved barrier properties in respect of water vapour, and somewhat improved barrier properties also against oxygen.
- Variations of the laminating material for the desired type of packaging laminate for beverages and liquids are thus found within the group of polyethylenes, i.e. polymers chosen from the group that includes low-density polyethylene (LDPE), high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and mixtures of two or more of these polymers.
- LDPE low-density polyethylene
- HDPE high-density polyethylene
- MDPE medium-density polyethylene
- LLDPE linear low-density polyethylene
- VLDPE very low-density polyethylenes
- ULDPE ultra low-density polyethylenes
- This group thus also includes copolymers of ethylene and other alpha-olefin monomers which of course include, for example, linear low-density polyethylenes (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE), also copolymers of ethylene and propylene in different proportions, for example so-called plastomers or elastomers of the type marketed by Dow under the names "Engage” and "Affinity”, and also terpolymers of ethylene, propylene and an alpha-olefin monomer having polyethylene-like properties.
- LLDPE linear low-density polyethylenes
- VLDPE very low-density polyethylenes
- ULDPE ultra low-density polyethylenes
- the polymer in the laminating material in the packaging laminate according to the invention comprises a low-density polyethylene (LDPE) which can be produced either by a polymerization reaction in an autoclave reactor or by a polymerization reaction in a tube reactor.
- LDPE low-density polyethylene
- a low-density polyethylene (LDPE) which is produced by polymerization in an autoclave can be extruded in a conventional manner without serious edge effects in the form of what is called neck-in, but it has limited draw-down properties, compared to LDPE produced in a tube reactor, i.e. compared to the other abovementioned polyethylene materials it has a higher melt elasticity, with corresponding MFI value, under the same processing conditions. It typically has a broad molecular weight distribution and long-chain branches in its molecular structure.
- Neck-in is understood as the drawing-in at the edges of a melt curtain of extruded polymer, which occurs between the outlet of the extrusion die and the first point of contact of the curtain with the running web of material that is to be coated with the polymer.
- the warm extruded molten film thus shrinks, such that its width shrinks on the way between the die and the nip between the cooling cylinders.
- the edge zones of the melt curtain thicken.
- the warm curtain is often extruded wider than the web that is to be coated, in order to reduce costs in respect of uncoated substrate material, which is often more expensive than the extruded polymer.
- the edge waste that is formed thus consists of only extruded material, which can be cut away and recycled.
- the width of the edge zones constitutes the measure of the neck-in in millimetres and is usually indicated as the combined uncoated width of both the edges.
- draw-down refers to the ability of the extruded melt curtain to hold together without breaks or gaps in the curtain as the melt is drawn with high acceleration down the web in the nip from the outlet of the extrusion die.
- LDPE produced in an autoclave reactor with an MFI of 4 to 10 g/10 min, measured as per ISO1133 at 2.16 kg and 190°C can be advantageously combined with adhesive layers of adhesive polymer with an MFI value of 4 to 10 g/10 min.
- LDPE produced in an autoclave reactor with an MFI of 4 to 10 g/10 min, measured as per ISO1133 at 2.16 kg and 190°C can advantageously be combined with adhesive layers of adhesive polymer with an MFI value of 10 to 20 g/10 min.
- LDPE produced in an autoclave reactor with an MFI of 10 to 20 g/10 min, measured as per ISO1133 at 2.16 kg and 190°C can advantageously be combined with adhesive layers of adhesive polymer with an MFI value of 4 to 10 g/10 min.
- a low-density polyethylene (LDPE) produced by polymerization in a tube reactor generally has a lower melt elasticity and is much more sensitive to negative edge effects, in the form of neck-in during conventional extrusion, than is a low-density polyethylene (LDPE) produced by polymerization in an autoclave reactor, and it therefore cannot be extruded without appreciable neck-in, which results in substantial edge waste from the web and, consequently, increased costs.
- LDPE low-density polyethylene
- a tube-produced LDPE also has long-chain branches, but it lacks the high proportion of molecules of high molecular weight which an autoclave-produced LDPE has and which can be seen as a "tail” or "extra top” at the end of a molecular weight distribution curve for autoclave-produced LDPE.
- a tube-produced LDPE generally has a lower melt elasticity than an autoclave-produced LDPE.
- an LDPE produced in a tube reactor can, despite this, be applied at relatively high extrusion speeds, for example 400 m/min and higher, in part by virtue of its better draw-down properties, even at lower temperatures, for example from 280 to 310, for example from 290 to 300°C.
- the layer in the laminating material with LDPE produced in a tube reactor can be extruded more thinly, in the method according to the invention, than in the case of conventional lamination with only LDPE as laminating material, and the total amount of laminating material can be reduced, sufficient or better adhesion can be achieved, and energy is saved.
- an LDPE produced by polymerization in an autoclave reactor can also be extruded at relatively high speed and also at lower temperature, despite its poorer draw-down properties, while at the same time the layers can be extruded more thinly, and the total amount of laminating material is reduced, better adhesion can be achieved, and energy is saved.
- An adhesive polymer material should be of a type which is intended for extrusion coating or extrusion lamination. At a lower extrusion temperature, in the method according to the invention, it is therefore possible to maintain the necessary adhesion and avoid negative edge effects, while at the same time the extrusion process is more energy-efficient and avoids the use of substances and methods that are harmful to health and to the environment.
- extrusion temperature is measured by an IR meter on the melt curtain immediately below the outlet of the die.
- Relatively high extrusion or lamination speed means web speeds from ca 400 m/min and upwards, while a lower speed means ca 100-300 m/min.
- Thin layers mean layers thinner than the thickness of 20 g/m 2 or thinner, which is normally required in conventional extrusion lamination with only LDPE as laminating material.
- the central layer of the laminating material according to the invention can have a thickness of from 10 to 14 g/m 2
- the outer adhesive polymer layers of the laminating material can each have a thickness of from 2 to 5 g/m 2 , for example 3 to 4 g/m 2 .
- the method according to the invention is especially advantageous for LDPE polymers that have been produced by polymerization in a tube reactor, in order to overcome the disadvantages thereof in the form of neck-in tendency, while at the same time other general advantages are obtained in the production of the packaging laminate, namely excellent adhesion, lower energy consumption, and advantages in terms of health and the environment.
- the packaging laminate according to the invention is in the same way advantageous for comprising linear polymers as laminating material, especially polyolefins with a linear molecular structure, compared to LDPE that has been produced by polymerization in a tube reactor, generally polyethylene polymers, since they have more or less the same processing properties in extrusion coating and their common feature is that they all have low melt elasticity and therefore a high tendency to neck-in at the edges of the melt curtain as compared to conventional autoclave-produced LDPE.
- the laminating material of the center layer thus comprises polyethylenes chosen from the group consisting of LDPE produced by polymerization in a tube reactor, high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts, or other catalysts, or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and mixtures of two or more of these polymers.
- HDPE high-density polyethylene
- MDPE medium-density polyethylene
- LLDPE linear low-density polyethylene
- VLDPE very low-density polyethylenes
- ULDPE ultra low-density polyethylenes
- a common feature of all these polymer types is that they have a lower melt elasticity with a corresponding MFI, in extrusion coating, as compared to autoclave-produced LDPE, the reason being that they have a narrower molecular weight distribution and/or a lower proportion of long-chain branches.
- the laminating material comprises polyethylenes chosen from the group consisting of LDPE produced by polymerization in a tube reactor, medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts, or other catalysts, or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and mixtures of two or more of these polymers.
- MDPE medium-density polyethylene
- LLDPE linear low-density polyethylene
- VLDPE very low-density polyethylenes
- ULDPE ultra low-density polyethylenes
- a common feature of all these polymer types is that they have a lower melt elasticity with a corresponding MFI, in extrusion coating, as compared to autoclave-produced LDPE, the reason being that they have a narrower molecular weight distribution and/or a lower proportion of long-chain branches.
- the linear polymers also provide a laminated packaging material according to the invention with better elastic properties, such as improved tear resistance and puncture resistance, and this results in packaging containers with improved integrity, i.e. improved durability to transport stresses.
- the laminating material thus comprises polyethylenes chosen from the group consisting of medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts, other catalysts, or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and mixtures of two or more of these polymers.
- MDPE medium-density polyethylene
- LLDPE linear low-density polyethylene
- VLDPE very low-density polyethylenes
- ULDPE ultra low-density polyethylenes
- Examples of usable polymers for the liquid-tight outer layers of the packaging laminate according to the invention are polyolefins, such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE), high-density polyethylene (HDPE) and polypropylene (PP).
- LDPE low-density polyethylene
- LLDPE linear low-density polyethylene
- VLDPE very low-density polyethylenes
- ULDPE ultra low-density polyethylenes
- HDPE high-density polyethylene
- PP polypropylene
- the outer layer on the inside of the packaging laminate i.e. the side to be directed towards a product packed in the packaging container, is advantageously bonded to the aluminium foil by a layer of an adhesive polymer.
- a usable adhesive for the packaging laminate according to the invention must from the very outset, and therefore without the need for additional measures, have active binding sites in the form of polar functional groups, according to one embodiment of the invention free carboxylic acid groups, by which the laminating material can effectively and permanently bind on the one hand to the paper or paperboard web and on the other hand to the material serving as gas barrier.
- the content of polar binding groups must be high enough to achieve adhesion with the aluminium foil and the paperboard layer, but not so high that the adhesive material loses compatibility with the central layer of the laminating material.
- a further requirement of a well-functioning adhesive polymer is that it can be extruded at a temperature which is high enough to achieve adhesion, but without initiating uncontrolled degradation reactions that impair quality.
- the temperature should rather not exceed 290 °C and at any rate not 300 °C.
- the adhesion between the first adhesive composition and the paper or paperboard is so high that it generates fibre tear within the paper or paperboard layer, upon adhesion testing according to ASTMD903-98(2010).
- the adhesion between the aluminium barrier layer and the laminating material is higher than 105 N/m, such as higher than 200 N/m.
- EAA ethylene-acrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA first-mentioned type
- EAA ethylene-methacrylic acid copolymer
- EAA first-mentioned type
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid copolymer
- EAA ethylene-methacrylic acid
- the same adhesive polymer in the adhesive layer on one surface of the central polymer layer as in the adhesive layer on the other surface of the central polymer layer is preferable, for reasons of processing technology, to use the same adhesive polymer in the adhesive layer on one surface of the central polymer layer as in the adhesive layer on the other surface of the central polymer layer, although the amounts of adhesive polymer in the respective adhesive layers can differ from each other.
- the adhesive polymer has an equivalent viscosity to, and therefore a melt flow index (MFI) at the same level as, an LDPE which is used in the central layer of the laminating material, intended for extrusion coating.
- MFI melt flow index
- the adhesive polymer has a lower viscosity than, and therefore a higher melt flow index (MFI) than, an LDPE which is used in the central layer of the laminating material, intended for extrusion coating.
- An adhesive layer containing free polar groups in the form of carboxylic acid groups may be characterised by methods including for example infrared spectroscopy (IR, FTIR).
- IR infrared spectroscopy
- a particular adhesive polymer having a particular monomeric composition will give rise to a characteristic absorption spectra with peaks representing different molecular groups of the monomers included.
- free carboxylic groups will give rise to a characteristic peak in the FTIR spectrum that corresponds to stretching vibration of the acid group at between 1710-1780 cm-1.
- the amount or concentration of such groups may be determined.
- Materials that have gas barrier properties, in particular against oxygen, and that are usable for the packaging laminate according to the invention may be an aluminium foil or a polymer film which, on one side, has a coating of metal, e.g. vapour-deposited aluminium.
- An aluminium foil is preferably chosen which, in addition to having excellent barrier properties against gases, in particular oxygen, also allows the packaging laminate to be sealed by induction sealing, which is a rapid, simple and effective heat-sealing technique.
- induction sealing which is a rapid, simple and effective heat-sealing technique.
- sealing can be carried out using an ultrasonic sealing technique, which is also a rapid, simple and effective heat-sealing technique.
- a packaging container is made available for oxygen-sensitive liquid food, for example milk, juice, wine and cooking oil.
- the packaging container is characterized in that it is produced from the packaging laminate according to the invention by folding and heat-sealing.
- the packaging container can be produced from a web of the packaging laminate according to the invention, by a process in which the web is firstly shaped into a tube by means of both lengthwise edges of the web being joined to each other in an overlap seam by melting together the mutually facing plastic layers, after which the tube is filled with the food product in question, e.g. milk, juice, wine or cooking oil, and is divided into contiguous pillow-shaped packaging units by repeated pressing-together and heat-sealing of the tube transversely with respect to the longitudinal direction of the tube, below the product level of the tube, which packaging units are separated from each other and are finally given the desired geometric shape, usually a shape like a brick, by means of at least one further forming and heat-sealing operation.
- the desired geometric shape usually a shape like a brick
- the packaging container can be produced from a tubular blank of the packaging laminate according to the invention that is folded flat, by first of all building the blank up to form an open tubular container capsule, of which one end is closed off by means of folding and heat-sealing of prepared integral end panels, which container capsule is filled with the food product in question, e.g. milk, juice, wine or cooking oil, through its open end, which is thereafter closed off by means of at least one further folding and heat-sealing of corresponding prepared integral end panels.
- the food product in question e.g. milk, juice, wine or cooking oil
- a method of manufacturing the packaging laminate of the invention wherein the layer of paper or paperboard is bonded to the layer serving as a gas or vapour barrier layer by means of melt extrusion lamination, such that a web of a the material with barrier properties is brought together with a web of the paper or paperboard, and the webs brought together are guided through a pressure nip between two adjacent rotatable cylinders, while at the same time a laminating material of molten polymer is applied into the nip between the webs in order to permanently bind these to each other when the molten polymer layer is solidified.
- the laminating material comprises several polymer materials
- they are separately extruded but brought together in the extrusion die to form a co-extruded polymer melt curtain, i.e. the paper or paperboard layer and the barrier layer are laminated to each other by melt co-extrusion lamination with the laminating material.
- the two liquid-tight and heat-sealable outer layers are applied by extrusion coating to both sides of the web by means of conventional and already installed extrusion equipment.
- at least one of the two liquid-tight and heat-sealable outer layers of polymer, in the packaging laminate is applied by film lamination, in which a prefabricated film of the polymer is laminated onto one surface of the web with the aid of a suitable adhesive that is applied between the web and the film.
- FIG. 1 shows schematically a cross section through an embodiment of a general packaging laminate of the invention.
- the packaging laminate designated by the general reference sign 10
- the packaging laminate 10 also has an outer liquid-tight coating 14, 15 on both sides of the paper or paperboard layer 11, the heat sealable layer 15 on the inside of the packaging laminate being aimed to be in direct contact with the filled food product on the inside of a packaging container.
- the heat sealable product contact layer 15 is optionally bonded to the barrier layer 12 by means of an inside adhesive polymer 16, the inside adhesive polymer preferably being a polymer having ethylene monomer units and some monomer units having carboxylic acid functionality, which amounts to from 1,4 to 3,0 mol% of the inside adhesive polymer.
- the laminating material layer 13 has a central layer 13a, of which one surface has a layer 13b of an adhesive with the ability to bind to the paper or paperboard layer 11, and of which the other surface has a layer 13c of an adhesive with the ability to bind to the layer 12 serving as gas barrier.
- the adhesive layer 13b on one side of the central layer 13a is in contact with the paper or paperboard layer 11, while the adhesive layer 13c on the other side of the central layer 13a is in contact with the layer 12 serving as gas barrier.
- the central layer 13a can be a polymer layer of low-density polyethylene (LDPE) that can be produced by a polymerization reaction in either an autoclave reactor or a tube reactor.
- a polymer layer of low-density polyethylene (LDPE) is preferably a low-density polyethylene (LDPE) that is produced in the latter type of reactor, i.e. a tube reactor, since a low-density polyethylene (LDPE) of this kind permits extrusion at a lower extrusion temperature and at a higher web speed (draw-down) than a low-density polyethylene (LDPE) that is produced in an autoclave reactor.
- LDPE low-density polyethylene
- the central layer 13a can be a polymer layer made of a linear polymer, which helps give the finished packaging laminate 10c improved mechanical properties when these are desired.
- linear polymers that can be used are high-density polyethylene (HDPE), or linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts or so-called single-site catalysts.
- a well-functioning adhesive polymer for the adhesive layers 13b and 13c has active binding sites (free carboxylic acid groups) to permit effective and permanent binding to the paper or paperboard layer 11 and to the layer 12 serving as gas barrier.
- a further requirement of a well-functioning adhesive polymer in the packaging laminate 10 is that it is able to be applied at a sufficiently low temperature in order to avoid loss of quality as a result of degradation reactions upon contact with the warmer polymer in the central layer 13a of the lamination layer 13.
- Practical examples of adhesive polymers with active binding sites (acid groups) are ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA) and blends thereof.
- the adhesive layers 13b and 13c of the lamination layer 13 can be made from adhesive polymers of different layer thicknesses, but they are preferably made from one and the same adhesive polymer with one and the same layer thickness.
- the first adhesive polymer of the first adhesive layer 13b is a copolymer having ethylene monomer units and monomer units having carboxylic acid functional groups at an amount of from 0,15 to 1,3 mol%, more preferably from 0,15 to 0,7 mol%, of the first adhesive polymer.
- the first adhesive layer 13b consists of an adhesive polymer, which is a copolymer comprising ethylene monomer units and monomer units having carboxylic acid functional groups at an amount of from 0,15 to 1,3 mol%, of the adhesive polymer.
- the second adhesive polymer layer (13c) has the same adhesive polymer composition as the first adhesive layer.
- the material in the layer 12 serving as gas barrier can be an aluminium foil which, in addition to its excellent barrier properties against gases, in particular oxygen, also makes the packaging laminate 10 heat-sealable by means of induction sealing, which is a rapid and also effective sealing technique.
- the outer liquid-tight coatings 14 and 15 of the packaging laminate 10 can be coatings of a polyolefin, such as polyethylene (PE) and polypropylene (PP).
- a polyolefin such as polyethylene (PE) and polypropylene (PP).
- PE polyethylene
- PP polypropylene
- a usable polyethylene (PE) are low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE) produced with conventional catalysts or so-called single-site catalysts, and high-density polyethylene (HDPE).
- an outer liquid-tight coating which is intended to be directed towards a food product packed in a packaging container, can be bonded to the barrier layer by a layer of an adhesive polymer of the same type as, or different from, the adhesive layers included in the laminating material 13.
- the inside adhesive polymer is, as stated above, a polymer having ethylene monomer units and some monomer units having carboxylic acid functionality, which amounts to from 1,4 to 3,0
- the packaging laminate 10 in Figure 1 can be produced in the manner shown schematically in Figure 2 .
- a web 201 of paper or paperboard is unwound from a storage reel 200, and a corresponding web 203 of a material with barrier properties against gases, in particular oxygen, is unwound from a storage reel 202.
- the two webs 201 and 203 are brought together with each other and are guided together through a nip between two adjacent rotatable cylinders 204 and 205, while at the same time a laminating material 206 is applied between the webs to laminate them to each other and thereby form a durable laminated web 208.
- the laminating material 13, 206 is applied by extrusion or co-extrusion by means of an extruder 207 arranged above the nip and will be described in more detail below.
- the laminated web 208 is then conveyed via guide rollers 209 and 210 towards and through a nip between two further adjacent rotatable cylinders 211 and 212, while at the same time one surface of the web 208 is provided with an outer liquid-tight coating 213 of extrusion-coated polymer.
- the other surface of the web 208 is provided with an outer liquid-tight coating 214 of extruded polymer.
- an outer liquid-tight coating 213 is applied to one surface of the web by extrusion with the aid of an extruder 215, and an outer liquid-tight coating 214 is applied to the other surface of the web 208 by extrusion with the aid of a corresponding extruder 216 arranged near the web 208.
- the web thus coated is finally wound up for onward transport and further handling in which it is formed into dimensionally stable packaging containers for oxygen-sensitive liquid food, e.g. milk, juice, wine and cooking oil, as will be described hereinbelow.
- oxygen-sensitive liquid food e.g. milk, juice, wine and cooking oil
- the laminating material 206 with which the web 203 of the material with barrier properties against gases, in particular oxygen, is laminated to the paper or paperboard web 201 is a three-layer structure as in Fig 1 and shown on an enlarged scale in Figure 2A .
- This three-layer structure has a central layer 206a of a polymer which, on one surface, has a first outer layer 206b of an adhesive polymer with the ability to bind to paper or paperboard and, on its other surface, has a second outer layer 206c of an adhesive polymer with the ability to bind to said material with barrier properties against gases, in particular oxygen.
- the three-layer structure serving as laminating material is preferably extruded by co-extrusion, in such a way that the outer adhesive layer 206b is brought into direct contact with the paper or paperboard web 201, while at the same time the outer adhesive layer 206c is brought into direct contact with the web 203 of the material with barrier properties against gases, in particular oxygen.
- a surface treatment such as ozone treatment or corona, or any further addition of chemicals to the lamination operation.
- the polymer for the central layer 206a of the laminating material 206 can be chosen more or less freely and is thus not limited to any particular type of polymer.
- An example of a usable polymer for the central layer 206a of the laminating material 206 is a low-density polyethylene (LDPE) of the type which is produced by a polymerization reaction in an autoclave reactor, or a low-density polyethylene (LDPE) of the type which is produced by a polymerization reaction in a tube reactor.
- LDPE low-density polyethylene
- LDPE low-density polyethylene
- low-density polyethylene (LDPE) produced in an autoclave reactor can, despite its poorer draw-down properties, also be extruded at a relatively high speed and even at lower temperatures, while at the same time the layers can be extruded more thinly, the total amount of laminating material is reduced, better adhesion can be achieved, and energy is saved.
- LDPE low-density polyethylene
- Low-density polyethylene (LDPE) produced in a tube reactor permits co-extrusion coating at a relatively high production speed, for example ca. 400 m/min and over, by virtue of its good draw-down properties, compared with an LDPE produced in an autoclave reactor. It also has the added advantage that it can be co-extruded and coated at a lower extrusion temperature, for example 280 to 310°C, for example 290 to 300°C, than LDPE produced in an autoclave reactor and therefore requires less energy than the latter. In turn, extrusion of low-density polyethylene (LDPE) at a lower temperature such as this reduces the risk of the quality being impaired by degradation reactions, as has already been mentioned. Furthermore, no surface treatment such as ozone treatment is needed.
- LDPE low-density polyethylene
- linear polymers which have the advantage of helping to improve the mechanical properties of the finished packaging laminate.
- linear polymers that can be used in the method according to the invention are high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts or so-called single-site catalysts, or constrained-geometry catalysts, including so-called metallocene catalysts.
- HDPE high-density polyethylene
- MDPE medium-density polyethylene
- LLDPE linear low-density polyethylene
- VLDPE very low-density polyethylenes
- ULDPE ultra low-density polyethylenes
- adhesive polymers having free, active carboxylic acid groups may be maleic-anhydride functionalised polyolefins, in particular maleic-anhydride functionalised polyethylenes, which also provide polyolefin-based polymers having free carboxylic acid functionality.
- adhesives that are different from each other can be used in the outer layers 206b and 206c of the laminating material 206, it is advantageous, for reasons of processing technology, to use adhesive of the same composition and of the same quantity in each of the outer layers 206b and 206c.
- Materials that have gas barrier properties and that are usable in the method according to the invention may be an aluminium foil or a polymer film which, on one or both of its sides, has a coating of metal, e.g. vapour-deposited or vacuum-metallized aluminium.
- An aluminium foil is preferably used which, in addition to having excellent barrier properties against gases, also allows the packaging laminate to be sealed by so-called induction sealing, which is a rapid, simple and effective heat-sealing technique.
- Examples of usable polymers for the liquid-tight, heat-sealable outer layers 213 and 214 applied to the web 208 in the method according to the invention are polyolefins, such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and polypropylene (PP).
- LDPE low-density polyethylene
- LLDPE linear low-density polyethylene
- HDPE high-density polyethylene
- PP polypropylene
- packaging laminate 10 in Figure 1 From a web of the packaging laminate 10 in Figure 1 for example, it is possible, to produce dimensionally stable packaging containers of a disposable type for oxygen-sensitive liquid foods, such as milk, juice, wine and cooking oil, by folding and heat-sealing in a manner known per se.
- Such packaging containers are nowadays produced with the aid of modern packaging machines of the type in which finished packages are shaped, filled and sealed.
- FIG. 3 One way in which packaging containers made of the packaging laminate 10 in Figure 1 can be shaped, filled and sealed is illustrated in Figure 3 .
- the so-called single-use packages are produced from a web by being shaped into a tube 31, in which the longitudinal edges 32, 32' of the web are joined to each other in an overlap seam 33 by melting together the mutually facing surfaces of the plastic layers 14 and 15.
- the tube is filled 34 with the food product in question and is divided into contiguous pillow-shaped packaging units 36 by repeated pressing-together and heat-sealing of the tube transversely with respect to the longitudinal direction 35 of the tube, below the product level of the tube, and the packaging units are separated from each other and finally given the desired geometric shape, usually a parallelepipedal shape like a brick, by means of at least one further folding and heat-sealing step.
- a well-known example of a single-use package of this type is the commercial package sold under the name Tetra Brik aseptic, which is shown in Figure 4 .
- Tetra Brik aseptic which is shown in Figure 4 .
- a unique feature of this commercial type of packaging is that it is produced more or less completely by folding and heat-sealing 41, 42 of the web-shaped packaging laminate, without the use of extra packaging parts such as separate tops and/or bottoms.
- Such packaging containers 40 can also be provided with a suitable opening arrangement 43, for example a screw cap which, when opened, penetrates and removes the packaging material and permits emptying of the packaged product.
- the laminated packaging laminate can have perforations in the paperboard layer that has been laminated in between the polymers and barrier layers of the laminate.
- a hole is punched in the laminated packaging material immediately before the filling process, after which the hole is provided with a tape or pull-tab, on both sides of the packaging material.
- an opening arrangement in the form of a hinge or screw cap can be applied on top of the covered hole.
- an opening arrangement is applied which is cast onto a punched hole directly during the filling process. It is not necessary to provide the packaging container with an opening device, it can also be torn open by means of a tear-perforation, or by cutting.
- packaging containers can be produced as above but have, as their final shape, the pillow shape that is obtained directly after the packaging units have been separated from each other and that is not therefore further shaped by folding.
- Such a package is generally produced using a thinner paperboard material and therefore entails greater demands on adhesion and integrity of the packaging material with regard to the lamination layers and also to the mechanical strength characteristics, in particular the elastic characteristics, of the polymer layers.
- An example of one such package is shown in Figure 5 .
- Packaging containers for oxygen-sensitive liquid food can also be produced from sheet-like blanks or prefabricated blanks of the packaging laminate 10 in Figure 1 .
- packages are produced by first of all building the blank up to form an open tubular container capsule, of which one open end is closed off by means of folding and heat-sealing of integral end panels.
- the thus closed container capsule is filled with the food product in question, e.g. juice, through its open end, which is thereafter closed off by means of further folding and heat-sealing of corresponding integral end panels.
- An example of a packaging container produced from sheet-like and tubular blanks is shown in Figure 6 and is a so-called gable-top package 60.
- packages of this type which have a moulded top and/or screw cap made of plastic.
- Packaging laminate 10 was produced with the composition indicated in the following table: Laminate layer Reference sign in figures Coating quantity, g/m 2 (reference example 1) Coating quantity, g/m 2 (Comparative Example 1) Low-density polyethylene (LDPE) 14 12 12 12 Paperboard 11 Ethylene-acrylic acid copolymer (EAA) 13b --- 3 (Primacor 3540 Dow; with about 3,2 mol-% carboxylic acid groups) Low-density polyethylene (LDPE) 13a 20 10 (Novex 19N730) (Novex 19N730) (Autoclave-LDPE) Ethylene-acrylic acid copolymer (EAA) 13c --- 3 (Primacor 3540 Dow) Aluminium foil 12 6.3 ⁇ m 6.3 ⁇ m Ethylene-acrylic acid copolymer (EAA) (not shown) 6 6 Blend of LDPE and m-LLDPE (weight ratio 30:70) 15 19 19 19 19 19 19
- Packaging laminate 10 was produced by co-extrusion of the material layers 13a-13c as a three-layer structure, with the material layers included in the sequence 13b/13a/13c. This co-extrusion could generally be carried out at an extrusion speed of 200 m/min and at an extrusion temperature of below 310 °C and without the use of ozone or other extra chemicals to achieve and maintain a permanent binding of the aluminium foil 12, serving as gas barrier, to the paper or paperboard layer 11 of the packaging laminate.
- the paperboard material used throughout was CLC/C material with a flexural stiffness of 260 mN.
- the three layers were able to be co-extruded at the temperatures 290 -310 - 290 °C and at a web speed of 650 m/min, with excellent (non-measurable, above the detection limit) adhesion to the paperboard layer or barrier layer.
- the known packaging laminate of the prior art constituting a further reference example 1
- a packaging laminate produced by the method according to Comparative Example 1 thus has considerable environmental and health-related advantages over a corresponding packaging laminate produced in the known way, i.e. without use of adhesive chemicals in direct contact with the paper or paperboard layer and with the layer serving as gas barrier, in this case the aluminium foil.
- a peel test strips of packaging laminate measuring 15 mm in width are cut, and the two layers between which the adherence is to be measured are separated/delaminated.
- the two flaps of the delaminated strips are clamped in a tension testing machine, where the strips are further delaminated under controlled conditions at a delamination angle of 90°.
- the force during the delamination is measured with a load cell, and the peel test value is indicated by the unit N/m.
- the method is a variation of ASTM D903 - 98 (2010) "Standard Test Method for Peel or Stripping Strength of Adhesive Bonds", with the difference that the specimen width is 15 mm instead of 25 mm and the delamination angle is 90° instead of 180°.
- Comparative Example 1 was repeated with the difference that PrimacorTM 3460 (having about 3,6-4,0 mol-% of carboxlic acid groups) was used as adhesive polymer in both outer layers 13b and 13c of the laminating material.
- Conventional autoclave-LDPE Novex 19N 730 was used as central layer. The three-layers were co-extruded at the temperature setting 290-290-290 °C and were able to be coated at a web speed of 500 m/min.
- Comparative Example 1 was repeated with the difference that Novex M21N (having a carboxylic acid group (methacrylic acid) content of about 0,4 mol-%) was used as adhesive polymer in both outer layers 13b and 13c of the laminating material.
- Conventional autoclave-LDPE Novex 19N 730 was used as central layer.
- the three-layers were co-extruded at the temperature setting 290- 310- 290 °C and were evenly coated at a web speed of 500 m/min, without using ozone treatment, and found to have lower adhesion to the adjacent paperboard layer as well as to the Aluminium foil.
- Comparative Example 1 was repeated with the difference that Novex M21N (having a carboxylic acid group (methacrylic acid) content of about 0,4 mol-%) was used as adhesive polymer in both outer layers 13b and 13c of the laminating material.
- Conventional autoclave-LDPE Novex 19N 730 was used as central layer.
- the three-layers were co-extruded at the temperature setting 310-310-310 °C and were evenly coated at a web speed of 500 m/min, without using ozone treatment.
- Example 4 The results from Example 4 were very positive, regarding adhesion to paperboard as well as to aluminium foil and regarding gel formation. Improved adhesion to the aluminium foil (above 200 N/m, i.e. inseparable, as in Comparative Example 1) was seen, and in particular the adhesion result to the paperboard was improved. There was no separation between the paperboard layer and the adhesive polymer layer, but tear within the fibrous paperboard layer, so-called "Fibre-tear". There was no trace of gel formation observed, neither in the adhesive layers nor in the extrusion equipment under the same conditions as in Example 3.
- an adhesive ethylene co-polymer having a lower carboxylic acid content makes it possible to manufacture improved packaging laminates, without gel particles in the adhesive polymer applied, but still with excellent adhesion between the laminating material and the paperboard surface, and without need for surface treatments such as ozone treatment.
- Similar packaging laminates having a higher acid content in the laminating material will either have too low adhesion to paperboard, or a high risk for gel degradation particles present in the adhesive layers. At continuous and industrial production of packaging laminates, this is an evident and notable improvement.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
- The present invention relates to a packaging laminate for a packaging container for oxygen-sensitive liquid or semi-liquid food, which packaging laminate comprises a layer of paper or paperboard, and a layer serving as a gas or vapour barrier layer, which layers are bonded to each other by a laminating material, comprising a first adhesive polymer composition in direct contact with the paper or paperboard, the first adhesive polymer composition comprising a polymer material having ethylene monomer units and some monomer units having carboxylic acid functional groups.
- The invention also relates to a packaging container for liquid or semi-food, which packaging container has been produced by folding and sealing the packaging laminate.
- In addition, the invention relates to a method of manufacturing such a packaging laminate.
- A known packaging laminate of the type described above generally has a layer of paper or paperboard and outer liquid-tight coatings of polyethylene (PE), preferably low-density polyethylene (LDPE). In order to give the packaging laminate barrier properties against gases, in particular oxygen, the packaging laminate additionally has at least one further layer of a material which provides such barrier properties and which is bonded to the paper or paperboard layer by a lamination layer, preferably low-density polyethylene (LDPE). Examples of materials for a further layer of this kind can be a layer or film containing a polymer with inherent barrier properties, for example a copolymer of ethylene and vinyl alcohol (EVOH) or a polyamide (PA), or a prefabricated film coated with a liquid-film-coated or vacuum-deposited or vapour-deposited layer having corresponding barrier properties mainly against gases but also against flavouring agents and water vapour. A common example of coated prefabricated films of this kind is that of oriented films of polyester, for example polyethylene terephthalate (PET) or polypropylene (PP), with a metallized layer or a layer coated by plasma-assisted vapour deposition. An aluminium foil is generally used which, in addition to having excellent barrier properties against gases, in particular oxygen, also has the advantageous property of allowing the packaging laminate to be heat-sealed by induction sealing, which is a rapid, simple and effective heat-sealing technique.
- The known packaging laminate is conventionally produced from a web of paper or paperboard which is unwound from a storage reel, while at the same time a web of aluminium is unwound from a corresponding storage reel. The two unwound webs are brought together with each other and are both guided through the nip between two adjacent rotatable cylinders, while at the same time a laminating material, usually low-density polyethylene (LDPE), is applied between the webs in order to permanently bind the aluminium web to the paper or paperboard web. The paper or paperboard web is thereafter provided on both sides with liquid-tight coatings of polyethylene, normally low-density polyethylene (LDPE), and is then wound up on finished packaging reels for onward transport and handling.
- Dimensionally stable packaging containers of the single-use type are produced from the packaging laminate with the aid of highly efficient packaging machines of the type that shape, fill and seal finished packages from a web or from prefabricated blanks of the packaging laminate.
- For example, from a web of the packaging laminate, packaging containers are produced by a process in which the web is firstly shaped into a tube by means of both lengthwise edges of the web being joined permanently to each other in an overlap seam by melting together the mutually facing plastic layers of the web. The tube is filled with the food product in question, e.g. milk or juice, and is divided into contiguous pillow-shaped packaging units by repeated pressing-together and heat-sealing of the tube transversely with respect to the longitudinal direction of the tube, below the product level of the tube. The pillow-shaped packaging units are separated from each other, by cuts made in the transverse sealing zones, and are finally given the desired geometric shape, usually a shape like a brick, by means of at least one further forming and heat-sealing operation.
- A packaging laminate of the known type permits the production of dimensionally stable packaging containers that are product-compatible and consumer-friendly and hold oxygen-sensitive liquid food, for example milk, juice, wine and cooking oil, but are nonetheless associated with disadvantages in terms of both the environment and also processing technology.
- For example, the low-density polyethylene (LDPE) used to bind the aluminium foil to the paper or paperboard layer is a non-polar polymer which in itself lacks natural binding sites for binding to corresponding binding sites on the surface of the aluminium foil. Therefore, in the known method, functional binding sites have to be created synthetically. In practice, this is done by a process in which low-density polyethylene (LDPE) is applied between the paper or paperboard web and the aluminium web by extrusion at a higher temperature (in this case at ca 330°C) than the temperature (ca 300°C) that is normally used for extrusion coating of low-density polyethylene, while at the same time ozone is added in order to initiate an oxidation reaction and form polar groups, including free carboxylic acid groups, via which the low-density polyethylene (LDPE) can bind to active binding sites on the surface of the aluminium foil. An extrusion at elevated temperature (ca 330°C) entails increased consumption of energy and, consequently, an increased emission of environmentally harmful greenhouse gases ("carbon footprint").
- An extrusion of low-density polyethylene (LDPE) at elevated temperature (ca 330°C), as in the known method, causes degradation reactions of the polyethylene molecule by chain-breaking and cross-linking reactions. Once they have actually started, these degradation reactions can proceed to such an extent that the desired ability of the polymer to maintain a permanent binding strength between the aluminium foil and the paper or paperboard layer is lost, and the mechanical strength is thereby also lost.
- Ozone, which is generally used as an agent for promoting oxidation and adherence, is itself a gas that is harmful to health and to environment, and it has to be handled with the utmost care in order to prevent the gas leaking out. Furthermore, the treatment of the polymer material surface may also lead to degradation reactions and low-molecular degradation products, why it is advantageous if such treatments and chemicals can be avoided in the lamination processes.
EP 1 118 459 A1 discloses a packaging laminate having the layer sequence paper/adhesive/AI/PET. In one example, the adhesive is an ethylene-maleic anhydride copolymer with maleic anhydride content of 1.5 wt% (0.4 mol%). - There is therefore a need to make available a packaging laminate of the type mentioned at the outset, without the problems and disadvantages of the type associated with the known technique described above.
- Furthermore, the ever increasing use of opening arrangements, which are designed to penetrate, tear open, pull- or push-tearing the laminated packaging material, puts increasing demands on packaging laminates for packaging containers for oxygen-sensitive liquid food.
- The use of pre-cut holes in the paperboard, which are later laminated over by the various polymer and barrier layers of the laminate, requires close to perfect adhesion between the layers within the laminate membrane area of the pre-cut holes, in order to avoid problems of possible air inclusions, ruptures, leakages problems and penetration of gas molecules into the product. Any occurrence of bad adhesion between the laminated layers, may thus be detrimental to the sterility and integrity of the package, i.e. the ability to resist penetration of gases, micro-organisms and other substances which may harm the packaged food product on the one hand, and the ability to keep tight around the packaged liquid product, not to leak out, on the other hand.
- It is therefore an object of the invention to meet these needs.
- It is an object of the invention to provide a packaging laminate having improved integrity/adhesion between the laminated layers, such that the laminated layers are well adhered to each other across the entire surfaces of the layers, also within possible regions of pre-cut paperboard holes, in which non-paperboard layers form a laminate membrane, in particular a good permanent functional binding between the gas barrier layer and the paper or paperboard layer of the packaging laminate.
- Another object is to provide a packaging laminate for a packaging container for oxygen-sensitive liquid food, of the type produced by folding and heat-sealing of the packaging laminate, which provides good packaging container integrity according to the above and to provide such packaging containers.
- A further object is to make available a method for producing the packaging laminate, which method can be carried out without unnecessarily excessive consumption of energy, and without the use of substances that are harmful to health and to the environment, in order to achieve and maintain a permanent functional binding between the gas barrier layer and the paper or paperboard layer of the packaging laminate.
- According to one aspect, the invention thus provides a packaging laminate for a packaging container for oxygen-sensitive liquid food, such as milk, juice, wine and cooking oil, which packaging laminate comprises a layer of paper or paperboard, and a layer which serves as gas barrier and is bonded to the paper or paperboard layer by a laminating material.
- The packaging laminate thus comprises a layer of paper or paperboard, and a layer of aluminium serving as a gas or vapour barrier layer, which layers are bonded to each other by a laminating material, comprising a central polymer layer which, on one surface, has a first adhesive layer of a first adhesive polymer composition with the ability to bind to the paper or paperboard layer and, on its other surface, has a second adhesive layer of a second adhesive polymer composition with the ability to bind to the layer of aluminium serving as gas barrier, wherein the first adhesive layer on one surface of the central polymer layer is in contact with the paper or paperboard layer, and wherein the second adhesive layer on the other surface of the central polymer layer is in contact with the layer of aluminium serving as gas or vapour barrier, the first adhesive polymer composition comprising ethylene monomer units and from 0,15 to below 1,5 mol%, of monomer units having carboxylic acid functional groups, of the total first adhesive polymer composition, and the second adhesive layer having the same adhesive polymer composition as the first adhesive layer.
- According to an embodiment, the amount of monomer units having carboxylic acid functional groups in the laminating material is from 0,15 to 1,3 mol%, such as from 0,3 to 0,7 mol%, such as from 0,15 to 0,4 mol%, of the total first adhesive polymer composition. To get high reliable adhesion to a paperboard surface, relatively high temperatures of the coating polymer melt are required. At higher carboxylic acid group content, the risk for gel-forming due to polymer degradation in the heated melting and extrusion equipment increases, as well as the formation of soot particles and degradation products in the extruded polymer layer. At a too low amount of carboxylic acid groups, there will naturally be fewer free bonding sites towards the adjacent surfaces and too low adhesion as a result.
- According to an embodiment of the packaging laminate, the first adhesive polymer composition further comprises a low density polyethylene (LDPE). Adhesive copolymers from ethylene and (meth)acrylic acid monomer units, having a higher carboxylic group content may be further diluted in a blend composition with LDPE, such that the right amount of carboxylic groups may be obtained for optimal bonding and melt processing properties. The composition comprises at least 40 weight percent of the adhesive polymer.
- According to a specific embodiment of the packaging laminate, the first adhesive polymer composition comprises an adhesive polymer selected from the group consisting of ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA) and blends thereof. The composition comprises at least 40 weight percent of the EAA and/or EMAA. Suitable such adhesive copolymers are found for example with the tradenames of Primacor, Nucrel or Escor.
- According to an embodiment of the packaging laminate, the first adhesive polymer composition comprises a low density polyethylene (LDPE) at an amount of up to 60 wt-%.
- The material layer serving as a barrier layer is aluminium. Most commonly, the barrier material is an aluminium foil, but it can also be a metallised polymer film, wherein gas and/or vapour barrier properties are at least partly contributed to the packaging laminate by the metallised layer.
- According to an embodiment of the packaging laminate, the material layer serving as a barrier layer is, on its opposite side, which is to form the inside of the packaging laminate in a packaging container, bonded to a heat sealable food product contact layer of polyethylene by an inside adhesive polymer, which is in direct contact with the barrier layer, the inside adhesive polymer consisting of a polymer having ethylene monomer units and monomer units having carboxylic acid functional groups, which amount to from 1,5 mol% and above, preferably from 1,5 mol% to 3,5 mol%, more preferably from 1,5 mol% to 3,3 mol%, of the inside adhesive polymer. According to an embodiment, the inside adhesive polymer is an ethylene acrylic acid copolymer (EAA). The higher levels of carboxylic acid functionality in the adhesive polymer bonding to the aluminium foil on the inside, compared to the adhesive polymer bonding to the paper or paperboard layer, are required in the case of packaging of liquid milk and juice. Especially in fruit and vegetable juices, there are so-called free fatty acids that may migrate from the packaged product into and through the inside heat sealable layers towards the aluminium foil barrier, where they are accumulated to high concentrations and acting detrimentally on the adhesion between the aluminium foil and the adjacent inside polymer layer. A higher carboxylic acid functionality in this adjacent inside adhesive polymer layer delays the deterioration of the adhesion to the aluminium foil further, thus extending the shelf life of the filled juice package. In the case of packaging of milk, the inside heat sealable polyolefin layers need to be extruded at a lower temperature in order to avoid off-taste generation in the filled milk product due to migrating low-molecular degradation products into the milk. By the co-extrusion together with a carboxylic acid functional adhesive to be adjacent to the Alfoil, sufficient adhesion of the inside layers to the Alfoil as well as to the innermost heat sealable polyolefin layer is obtainable, although the extrusion temperature may need to be kept rather low.
- According to a further embodiment of the packaging laminate, the heat sealable food product contact layer comprises or consists of a polyethylene selected from the group consisting of LDPE, linear low density polyethylene (LLDPE) and linear low density polyethylene polymerised by a single site catalyst (m-LLDPE), and blends of two or more thereof.
- According to a further embodiment, the laminating material comprises a central polymer layer which, on one surface, has a first adhesive layer of a first adhesive polymer with the ability to bind to the paper or paperboard layer and, on its other surface, has a second adhesive layer of a second adhesive polymer with the ability to bind to the layer serving as gas barrier, wherein the first adhesive layer on one surface of the central polymer layer is in contact with the paper or paperboard layer, and wherein the second adhesive layer on the other surface of the central polymer layer is in contact with the layer of aluminium serving as gas or vapour barrier, the first adhesive polymer comprising ethylene monomer units and monomer units having carboxylic acid functional groups, which amount to from 0,15 to below 1,5 mol%, preferably from 0,15 to 1,3 mol%, more preferably from 0,15 to 0,7 mol%, most preferably from 0,15 to 0,4 mol%, of the first adhesive polymer, the second adhesive polymer layer having the same adhesive polymer composition as the first adhesive polymer layer.
- According to an embodiment, the first adhesive polymer comprises an adhesive polymer selected from the group consisting of ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA) and blends thereof.
- According to a further embodiment, the central polymer layer comprises a non-polar polymer material, such as a polyolefin.
- The first and second adhesive layers of the lamination material can be made from adhesive polymers of different layer thicknesses, but they are preferably made from one and the same adhesive polymer with one and the same layer thickness. The first adhesive polymer of the first adhesive layer may be a copolymer having ethylene monomer units and monomer units having carboxylic acid functional groups at an amount of from 0,15 to 1,5 mol%, such as from 0,15 to 1,3 mol%, such as from 0,15 to 0,7 mol%, of the first adhesive polymer.
- The second layer of a second adhesive polymer thus has the same composition as the first adhesive polymer. The advantage is not only that a simpler extrusion equipment may be used, by handling only one adhesive polymer melt for supplying the two adhesive layers of the laminate material, but also that gelling problems in the melt extrusion operation of the laminate material layers may be avoided while still achieving good adhesion between all layers concerned.
- According to one embodiment of the invention, the central polymer layer in the laminating material comprises a polyethylene. Within the group of polyethylenes, the properties of the central layer can be varied and tailored to achieve various final properties in a packaging laminate.
- Examples of linear polymers that can help to improve the mechanical properties of the finished packaging laminate, when they are included in a laminating layer, are so-called linear polymers, for example polyolefins, such as polyethylenes, for example high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and polypropylene (PP). Very low density polyethylene (VLDPE) and ultra low density polyethylene (ULDPE) are examples of subcategories within the category of linear low density polyethylenes. Linear polymers are understood as polymers which have a more linear molecular structure than LDPE, i.e. which have fewer long-chain branches. Depending on the type and quantity of comonomer, these polymers generally have greater durability in several respects. Depending on what is required of the finished packaging laminate as regards various mechanical properties, for example tear resistance, puncture resistance and durability, it is possible, according to the invention, for the laminating material and the adhesive polymer to be combined and varied within the context of suitable processing properties in extrusion coating and extrusion lamination. Mechanical, elastic properties of this kind are achieved with polyethylenes of the types MDPE, LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) and m-LLDPE, while HDPE generally gives, for example, improved barrier properties in respect of water vapour, and somewhat improved barrier properties also against oxygen.
- Variations of the laminating material for the desired type of packaging laminate for beverages and liquids are thus found within the group of polyethylenes, i.e. polymers chosen from the group that includes low-density polyethylene (LDPE), high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and mixtures of two or more of these polymers. This group thus also includes copolymers of ethylene and other alpha-olefin monomers which of course include, for example, linear low-density polyethylenes (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE), also copolymers of ethylene and propylene in different proportions, for example so-called plastomers or elastomers of the type marketed by Dow under the names "Engage" and "Affinity", and also terpolymers of ethylene, propylene and an alpha-olefin monomer having polyethylene-like properties.
- According to one embodiment of the invention, the polymer in the laminating material in the packaging laminate according to the invention comprises a low-density polyethylene (LDPE) which can be produced either by a polymerization reaction in an autoclave reactor or by a polymerization reaction in a tube reactor. A low-density polyethylene (LDPE) which is produced by polymerization in an autoclave can be extruded in a conventional manner without serious edge effects in the form of what is called neck-in, but it has limited draw-down properties, compared to LDPE produced in a tube reactor, i.e. compared to the other abovementioned polyethylene materials it has a higher melt elasticity, with corresponding MFI value, under the same processing conditions. It typically has a broad molecular weight distribution and long-chain branches in its molecular structure.
- Neck-in is understood as the drawing-in at the edges of a melt curtain of extruded polymer, which occurs between the outlet of the extrusion die and the first point of contact of the curtain with the running web of material that is to be coated with the polymer. The warm extruded molten film thus shrinks, such that its width shrinks on the way between the die and the nip between the cooling cylinders. At the same time, the edge zones of the melt curtain thicken. In order to overcome this problem, the warm curtain is often extruded wider than the web that is to be coated, in order to reduce costs in respect of uncoated substrate material, which is often more expensive than the extruded polymer. The edge waste that is formed thus consists of only extruded material, which can be cut away and recycled. The width of the edge zones constitutes the measure of the neck-in in millimetres and is usually indicated as the combined uncoated width of both the edges.
- The term draw-down refers to the ability of the extruded melt curtain to hold together without breaks or gaps in the curtain as the melt is drawn with high acceleration down the web in the nip from the outlet of the extrusion die. These properties of a polymer melt depend on its balance between viscous and elastic properties and can be summarized by the term "melt elasticity". This balance is a result of a number of polymer characteristics, mainly the molecular weight distribution and long-chain branching.
- According to an embodiment, LDPE produced in an autoclave reactor with an MFI of 4 to 10 g/10 min, measured as per ISO1133 at 2.16 kg and 190°C, can be advantageously combined with adhesive layers of adhesive polymer with an MFI value of 4 to 10 g/10 min. According to one embodiment of the invention, LDPE produced in an autoclave reactor with an MFI of 4 to 10 g/10 min, measured as per ISO1133 at 2.16 kg and 190°C, can advantageously be combined with adhesive layers of adhesive polymer with an MFI value of 10 to 20 g/10 min. According to one embodiment, LDPE produced in an autoclave reactor with an MFI of 10 to 20 g/10 min, measured as per ISO1133 at 2.16 kg and 190°C, can advantageously be combined with adhesive layers of adhesive polymer with an MFI value of 4 to 10 g/10 min.
- A low-density polyethylene (LDPE) produced by polymerization in a tube reactor generally has a lower melt elasticity and is much more sensitive to negative edge effects, in the form of neck-in during conventional extrusion, than is a low-density polyethylene (LDPE) produced by polymerization in an autoclave reactor, and it therefore cannot be extruded without appreciable neck-in, which results in substantial edge waste from the web and, consequently, increased costs.
- A tube-produced LDPE also has long-chain branches, but it lacks the high proportion of molecules of high molecular weight which an autoclave-produced LDPE has and which can be seen as a "tail" or "extra top" at the end of a molecular weight distribution curve for autoclave-produced LDPE. A tube-produced LDPE generally has a lower melt elasticity than an autoclave-produced LDPE.
- With the method of co-extruding layers of the laminating material, an LDPE produced in a tube reactor can, despite this, be applied at relatively high extrusion speeds, for example 400 m/min and higher, in part by virtue of its better draw-down properties, even at lower temperatures, for example from 280 to 310, for example from 290 to 300°C. At the same time, the layer in the laminating material with LDPE produced in a tube reactor can be extruded more thinly, in the method according to the invention, than in the case of conventional lamination with only LDPE as laminating material, and the total amount of laminating material can be reduced, sufficient or better adhesion can be achieved, and energy is saved. By virtue of the method according to the invention, an LDPE produced by polymerization in an autoclave reactor can also be extruded at relatively high speed and also at lower temperature, despite its poorer draw-down properties, while at the same time the layers can be extruded more thinly, and the total amount of laminating material is reduced, better adhesion can be achieved, and energy is saved.
- By means of the method according to the invention, differences in the behaviour of the two polymer types upon extrusion can be effectively counteracted and even eliminated by a suitable choice of the outer adhesive layers of the laminating material. An adhesive polymer material should be of a type which is intended for extrusion coating or extrusion lamination. At a lower extrusion temperature, in the method according to the invention, it is therefore possible to maintain the necessary adhesion and avoid negative edge effects, while at the same time the extrusion process is more energy-efficient and avoids the use of substances and methods that are harmful to health and to the environment. By co-extruding the central layer of the laminating material with the outer adhesive layers on both sides, a more stable melt curtain of polymer is obtained, and the various properties of the laminating materials in respect of neck-in and draw-down can compensate each other at lower extrusion temperatures, and lamination of material can take place at relatively high speed, while at the same time good or better adhesion can be achieved, and thin layers of the respective polymer layers can be applied without defects, such that the total costs for raw material and laminating steps in the production are maintained or even reduced. Lower extrusion temperatures mean temperatures that are more than 15 degrees lower than the temperature used in conventional extrusion lamination with only LDPE as laminating material, i.e. 325-330°C, for example 280-310°C, for example 290-310°C. The extrusion temperature is measured by an IR meter on the melt curtain immediately below the outlet of the die. Relatively high extrusion or lamination speed means web speeds from ca 400 m/min and upwards, while a lower speed means ca 100-300 m/min. Thin layers mean layers thinner than the thickness of 20 g/m2 or thinner, which is normally required in conventional extrusion lamination with only LDPE as laminating material. The central layer of the laminating material according to the invention can have a thickness of from 10 to 14 g/m2, while the outer adhesive polymer layers of the laminating material can each have a thickness of from 2 to 5 g/m2, for example 3 to 4 g/m2.
- The method according to the invention is especially advantageous for LDPE polymers that have been produced by polymerization in a tube reactor, in order to overcome the disadvantages thereof in the form of neck-in tendency, while at the same time other general advantages are obtained in the production of the packaging laminate, namely excellent adhesion, lower energy consumption, and advantages in terms of health and the environment.
- The packaging laminate according to the invention is in the same way advantageous for comprising linear polymers as laminating material, especially polyolefins with a linear molecular structure, compared to LDPE that has been produced by polymerization in a tube reactor, generally polyethylene polymers, since they have more or less the same processing properties in extrusion coating and their common feature is that they all have low melt elasticity and therefore a high tendency to neck-in at the edges of the melt curtain as compared to conventional autoclave-produced LDPE.
- According to one embodiment of the invention, the laminating material of the center layer thus comprises polyethylenes chosen from the group consisting of LDPE produced by polymerization in a tube reactor, high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts, or other catalysts, or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and mixtures of two or more of these polymers. A common feature of all these polymer types is that they have a lower melt elasticity with a corresponding MFI, in extrusion coating, as compared to autoclave-produced LDPE, the reason being that they have a narrower molecular weight distribution and/or a lower proportion of long-chain branches.
- According to one embodiment of the invention, the laminating material comprises polyethylenes chosen from the group consisting of LDPE produced by polymerization in a tube reactor, medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts, or other catalysts, or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and mixtures of two or more of these polymers. A common feature of all these polymer types is that they have a lower melt elasticity with a corresponding MFI, in extrusion coating, as compared to autoclave-produced LDPE, the reason being that they have a narrower molecular weight distribution and/or a lower proportion of long-chain branches. The linear polymers also provide a laminated packaging material according to the invention with better elastic properties, such as improved tear resistance and puncture resistance, and this results in packaging containers with improved integrity, i.e. improved durability to transport stresses.
- According to one embodiment of the invention, the laminating material thus comprises polyethylenes chosen from the group consisting of medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts, other catalysts, or with so-called single-site catalysts or constrained-geometry catalysts, including so-called metallocene-LLDPE (m-LLDPE) catalysts, and mixtures of two or more of these polymers.
- Examples of usable polymers for the liquid-tight outer layers of the packaging laminate according to the invention are polyolefins, such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE), high-density polyethylene (HDPE) and polypropylene (PP). In cases where the barrier layer is made of aluminium foil, the outer layer on the inside of the packaging laminate, i.e. the side to be directed towards a product packed in the packaging container, is advantageously bonded to the aluminium foil by a layer of an adhesive polymer.
- This results in even better adhesion between all the layers of the packaging laminate and in good durability of the filled packaging containers, for example during transport and handling.
- As has been mentioned above, a usable adhesive for the packaging laminate according to the invention must from the very outset, and therefore without the need for additional measures, have active binding sites in the form of polar functional groups, according to one embodiment of the invention free carboxylic acid groups, by which the laminating material can effectively and permanently bind on the one hand to the paper or paperboard web and on the other hand to the material serving as gas barrier. The content of polar binding groups must be high enough to achieve adhesion with the aluminium foil and the paperboard layer, but not so high that the adhesive material loses compatibility with the central layer of the laminating material. A further requirement of a well-functioning adhesive polymer is that it can be extruded at a temperature which is high enough to achieve adhesion, but without initiating uncontrolled degradation reactions that impair quality. For Primacor 3540, used in the Examples, the temperature should rather not exceed 290 °C and at any rate not 300 °C.
- It is generally much harder to obtain good adhesion between a polymer and the paperboard surface than between the polymer and the surface of an aluminium foil. When extrusion coating an LDPE onto paperboard, various surface activation treatments are necessary in the lamination operation, as well as a high extrusion temperature of 220-225 °C. In some embodiments, the adhesion between the first adhesive composition and the paper or paperboard is so high that it generates fibre tear within the paper or paperboard layer, upon adhesion testing according to ASTMD903-98(2010). In some embodiments, the adhesion between the aluminium barrier layer and the laminating material is higher than 105 N/m, such as higher than 200 N/m.
- Examples of adhesives that meet the above requirements are an ethylene-acrylic acid copolymer (EAA) and an ethylene-methacrylic acid copolymer (EMAA), which both include free carboxylic acid groups by which they can bind effectively and permanently to the respective adjacent layer in the packaging laminate. A practical example of the first-mentioned type (EAA) is commercially available under the trade name Primacor from Dow Chemical Company, and a corresponding example of the latter type (EMAA) can be obtained from DuPont under the trade name Nucrel. A further example of a usable adhesive is the one sold by ExxonMobil Chemicals under the trade name Escor. According to an embodiment, it is preferable, for reasons of processing technology, to use the same adhesive polymer in the adhesive layer on one surface of the central polymer layer as in the adhesive layer on the other surface of the central polymer layer, although the amounts of adhesive polymer in the respective adhesive layers can differ from each other. However, according to an embodiment, it is possible to use different adhesive polymers in the two layers, if so desired, in order to achieve particular properties.
- According to one embodiment of the invention, the adhesive polymer has an equivalent viscosity to, and therefore a melt flow index (MFI) at the same level as, an LDPE which is used in the central layer of the laminating material, intended for extrusion coating. According to one embodiment of the invention, the adhesive polymer has a lower viscosity than, and therefore a higher melt flow index (MFI) than, an LDPE which is used in the central layer of the laminating material, intended for extrusion coating.
- An adhesive layer containing free polar groups in the form of carboxylic acid groups, may be characterised by methods including for example infrared spectroscopy (IR, FTIR). A particular adhesive polymer having a particular monomeric composition, will give rise to a characteristic absorption spectra with peaks representing different molecular groups of the monomers included. In particular free carboxylic groups will give rise to a characteristic peak in the FTIR spectrum that corresponds to stretching vibration of the acid group at between 1710-1780 cm-1. By a calibration curve, the amount or concentration of such groups may be determined.
- Materials that have gas barrier properties, in particular against oxygen, and that are usable for the packaging laminate according to the invention may be an aluminium foil or a polymer film which, on one side, has a coating of metal, e.g. vapour-deposited aluminium. An aluminium foil is preferably chosen which, in addition to having excellent barrier properties against gases, in particular oxygen, also allows the packaging laminate to be sealed by induction sealing, which is a rapid, simple and effective heat-sealing technique. Alternatively, sealing can be carried out using an ultrasonic sealing technique, which is also a rapid, simple and effective heat-sealing technique.
- In another aspect of the invention, a packaging container is made available for oxygen-sensitive liquid food, for example milk, juice, wine and cooking oil. The packaging container is characterized in that it is produced from the packaging laminate according to the invention by folding and heat-sealing.
- For example, the packaging container can be produced from a web of the packaging laminate according to the invention, by a process in which the web is firstly shaped into a tube by means of both lengthwise edges of the web being joined to each other in an overlap seam by melting together the mutually facing plastic layers, after which the tube is filled with the food product in question, e.g. milk, juice, wine or cooking oil, and is divided into contiguous pillow-shaped packaging units by repeated pressing-together and heat-sealing of the tube transversely with respect to the longitudinal direction of the tube, below the product level of the tube, which packaging units are separated from each other and are finally given the desired geometric shape, usually a shape like a brick, by means of at least one further forming and heat-sealing operation.
- In an alternative embodiment, the packaging container can be produced from a tubular blank of the packaging laminate according to the invention that is folded flat, by first of all building the blank up to form an open tubular container capsule, of which one end is closed off by means of folding and heat-sealing of prepared integral end panels, which container capsule is filled with the food product in question, e.g. milk, juice, wine or cooking oil, through its open end, which is thereafter closed off by means of at least one further folding and heat-sealing of corresponding prepared integral end panels.
- In yet another aspect of the invention, a method of manufacturing the packaging laminate of the invention, wherein the layer of paper or paperboard is bonded to the layer serving as a gas or vapour barrier layer by means of melt extrusion lamination, such that a web of a the material with barrier properties is brought together with a web of the paper or paperboard, and the webs brought together are guided through a pressure nip between two adjacent rotatable cylinders, while at the same time a laminating material of molten polymer is applied into the nip between the webs in order to permanently bind these to each other when the molten polymer layer is solidified. In the case when the laminating material comprises several polymer materials, they are separately extruded but brought together in the extrusion die to form a co-extruded polymer melt curtain, i.e. the paper or paperboard layer and the barrier layer are laminated to each other by melt co-extrusion lamination with the laminating material.
- According to one embodiment of the method of the invention, the two liquid-tight and heat-sealable outer layers are applied by extrusion coating to both sides of the web by means of conventional and already installed extrusion equipment. In another embodiment, at least one of the two liquid-tight and heat-sealable outer layers of polymer, in the packaging laminate, is applied by film lamination, in which a prefabricated film of the polymer is laminated onto one surface of the web with the aid of a suitable adhesive that is applied between the web and the film.
- The invention will be described in more detail with reference to the attached drawings, in which:
-
Figure 1 is a schematic cross-sectional view of a packaging laminate according to the invention; -
Figure 2 schematically illustrates the production of the packaging laminate fromFigure 1 by the method according to the invention; -
Figure 2A is an enlarged view of the circled area A inFigure 2 when the packaging laminate ofFig. 1 is produced; -
Figure 3 schematically depicts a method for forming, filling and sealing packaging containers from a web on a reel of packaging material; -
Figure 4 is a schematic perspective view of a packaging container of the type Tetra Brik Aseptic, made from the packaging laminate according to the invention; -
Figure 5 is a schematic perspective view of a packaging container of the type Tetra Fino Aseptic, made from the packaging laminate according to the invention; and -
Figure 6 is a schematic perspective view of a packaging container of the gable-top type, a so-called Tetra Rex package, made from the packaging laminate according to the invention. -
Figure 1 shows schematically a cross section through an embodiment of a general packaging laminate of the invention. The packaging laminate, designated by the general reference sign 10, has alayer 11 of paper or paperboard, and alayer 12 which serves as gas or vapour barrier and is bonded to the paper orpaperboard layer 11 by alaminating material 13. In the embodiment shown, the packaging laminate 10 also has an outer liquid-tight coating paperboard layer 11, theheat sealable layer 15 on the inside of the packaging laminate being aimed to be in direct contact with the filled food product on the inside of a packaging container. The heat sealableproduct contact layer 15 is optionally bonded to thebarrier layer 12 by means of an insideadhesive polymer 16, the inside adhesive polymer preferably being a polymer having ethylene monomer units and some monomer units having carboxylic acid functionality, which amounts to from 1,4 to 3,0 mol% of the inside adhesive polymer. - The
laminating material layer 13 has acentral layer 13a, of which one surface has alayer 13b of an adhesive with the ability to bind to the paper orpaperboard layer 11, and of which the other surface has alayer 13c of an adhesive with the ability to bind to thelayer 12 serving as gas barrier. As is shown inFigure 1 , theadhesive layer 13b on one side of thecentral layer 13a is in contact with the paper orpaperboard layer 11, while theadhesive layer 13c on the other side of thecentral layer 13a is in contact with thelayer 12 serving as gas barrier. - In one illustrative embodiment according to the invention, the
central layer 13a can be a polymer layer of low-density polyethylene (LDPE) that can be produced by a polymerization reaction in either an autoclave reactor or a tube reactor. As has already been mentioned, a polymer layer of low-density polyethylene (LDPE) is preferably a low-density polyethylene (LDPE) that is produced in the latter type of reactor, i.e. a tube reactor, since a low-density polyethylene (LDPE) of this kind permits extrusion at a lower extrusion temperature and at a higher web speed (draw-down) than a low-density polyethylene (LDPE) that is produced in an autoclave reactor. - In another illustrative embodiment, the
central layer 13a can be a polymer layer made of a linear polymer, which helps give thefinished packaging laminate 10c improved mechanical properties when these are desired. Examples of linear polymers that can be used are high-density polyethylene (HDPE), or linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts or so-called single-site catalysts. - As has already been mentioned, a well-functioning adhesive polymer for the
adhesive layers paperboard layer 11 and to thelayer 12 serving as gas barrier. A further requirement of a well-functioning adhesive polymer in the packaging laminate 10 is that it is able to be applied at a sufficiently low temperature in order to avoid loss of quality as a result of degradation reactions upon contact with the warmer polymer in thecentral layer 13a of thelamination layer 13. Practical examples of adhesive polymers with active binding sites (acid groups) are ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA) and blends thereof. - The adhesive layers 13b and 13c of the
lamination layer 13 can be made from adhesive polymers of different layer thicknesses, but they are preferably made from one and the same adhesive polymer with one and the same layer thickness. The first adhesive polymer of the firstadhesive layer 13b is a copolymer having ethylene monomer units and monomer units having carboxylic acid functional groups at an amount of from 0,15 to 1,3 mol%, more preferably from 0,15 to 0,7 mol%, of the first adhesive polymer. The firstadhesive layer 13b consists of an adhesive polymer, which is a copolymer comprising ethylene monomer units and monomer units having carboxylic acid functional groups at an amount of from 0,15 to 1,3 mol%, of the adhesive polymer. The second adhesive polymer layer (13c) has the same adhesive polymer composition as the first adhesive layer. - According to the invention, the material in the
layer 12 serving as gas barrier can be an aluminium foil which, in addition to its excellent barrier properties against gases, in particular oxygen, also makes the packaging laminate 10 heat-sealable by means of induction sealing, which is a rapid and also effective sealing technique. - The outer liquid-
tight coatings laminating material 13. For the best performance of the packaging laminate, the inside adhesive polymer is, as stated above, a polymer having ethylene monomer units and some monomer units having carboxylic acid functionality, which amounts to from 1,4 to 3,0 mol% of the inside adhesive polymer. - The packaging laminate 10 in
Figure 1 , can be produced in the manner shown schematically inFigure 2 . Aweb 201 of paper or paperboard is unwound from astorage reel 200, and acorresponding web 203 of a material with barrier properties against gases, in particular oxygen, is unwound from astorage reel 202. The twowebs rotatable cylinders laminating material 206 is applied between the webs to laminate them to each other and thereby form a durablelaminated web 208. - In the example shown, the
laminating material extruder 207 arranged above the nip and will be described in more detail below. - The
laminated web 208 is then conveyed viaguide rollers rotatable cylinders 211 and 212, while at the same time one surface of theweb 208 is provided with an outer liquid-tight coating 213 of extrusion-coated polymer. In a subsequent nip between another two adjacentrotatable cylinders 217 and 218, the other surface of theweb 208 is provided with an outer liquid-tight coating 214 of extruded polymer. These two extrusion-coating steps can be carried out in reverse order and also, wholly or partly, before the lamination step in the nip between thecylinders - In the example shown, an outer liquid-
tight coating 213 is applied to one surface of the web by extrusion with the aid of anextruder 215, and an outer liquid-tight coating 214 is applied to the other surface of theweb 208 by extrusion with the aid of a corresponding extruder 216 arranged near theweb 208. - Following further mechanical or other machining operations on the web thus coated, the latter is finally wound up for onward transport and further handling in which it is formed into dimensionally stable packaging containers for oxygen-sensitive liquid food, e.g. milk, juice, wine and cooking oil, as will be described hereinbelow.
- Thus, the
laminating material 206 with which theweb 203 of the material with barrier properties against gases, in particular oxygen, is laminated to the paper orpaperboard web 201 is a three-layer structure as inFig 1 and shown on an enlarged scale inFigure 2A . This three-layer structure has acentral layer 206a of a polymer which, on one surface, has a firstouter layer 206b of an adhesive polymer with the ability to bind to paper or paperboard and, on its other surface, has a secondouter layer 206c of an adhesive polymer with the ability to bind to said material with barrier properties against gases, in particular oxygen. According to the invention, the three-layer structure serving as laminating material is preferably extruded by co-extrusion, in such a way that the outeradhesive layer 206b is brought into direct contact with the paper orpaperboard web 201, while at the same time the outeradhesive layer 206c is brought into direct contact with theweb 203 of the material with barrier properties against gases, in particular oxygen. There is no need for a surface treatment, such as ozone treatment or corona, or any further addition of chemicals to the lamination operation. - The polymer for the
central layer 206a of thelaminating material 206 can be chosen more or less freely and is thus not limited to any particular type of polymer. An example of a usable polymer for thecentral layer 206a of thelaminating material 206 is a low-density polyethylene (LDPE) of the type which is produced by a polymerization reaction in an autoclave reactor, or a low-density polyethylene (LDPE) of the type which is produced by a polymerization reaction in a tube reactor. By virtue of the method according to the invention, low-density polyethylene (LDPE) produced in an autoclave reactor can, despite its poorer draw-down properties, also be extruded at a relatively high speed and even at lower temperatures, while at the same time the layers can be extruded more thinly, the total amount of laminating material is reduced, better adhesion can be achieved, and energy is saved. - Low-density polyethylene (LDPE) produced in a tube reactor permits co-extrusion coating at a relatively high production speed, for example ca. 400 m/min and over, by virtue of its good draw-down properties, compared with an LDPE produced in an autoclave reactor. It also has the added advantage that it can be co-extruded and coated at a lower extrusion temperature, for example 280 to 310°C, for example 290 to 300°C, than LDPE produced in an autoclave reactor and therefore requires less energy than the latter. In turn, extrusion of low-density polyethylene (LDPE) at a lower temperature such as this reduces the risk of the quality being impaired by degradation reactions, as has already been mentioned. Furthermore, no surface treatment such as ozone treatment is needed.
- Other examples of usable polymers for the
central layer 206a of thelaminating material 206 are linear polymers, which have the advantage of helping to improve the mechanical properties of the finished packaging laminate. Examples of linear polymers that can be used in the method according to the invention are high-density polyethylene (HDPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE) produced with conventional catalysts or so-called single-site catalysts, or constrained-geometry catalysts, including so-called metallocene catalysts. - The requirement to be met by usable adhesive polymers for both
outer layers laminating material 206 is of course that they must permit effective and permanent binding to therespective web laminating material 206 such that it exceeds the critical temperature at which uncontrolled degradation reactions may be initiated that impair quality. Examples of adhesives that meet both of these requirements are ones which, in their natural state, have active acid groups on their surface, for example ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA). Such an adhesive is commercially available under the trade name Primacor from Dow Chemical Company, and another such adhesive can be obtained from DuPont under the trade name Nucrel. A further example is obtainable from ExxonMobil Chemicals under the trade name Escor. - Other examples of adhesive polymers having free, active carboxylic acid groups, suitable for some aspects of the present invention, may be maleic-anhydride functionalised polyolefins, in particular maleic-anhydride functionalised polyethylenes, which also provide polyolefin-based polymers having free carboxylic acid functionality.
- Although adhesives that are different from each other can be used in the
outer layers laminating material 206, it is advantageous, for reasons of processing technology, to use adhesive of the same composition and of the same quantity in each of theouter layers - Materials that have gas barrier properties and that are usable in the method according to the invention may be an aluminium foil or a polymer film which, on one or both of its sides, has a coating of metal, e.g. vapour-deposited or vacuum-metallized aluminium. An aluminium foil is preferably used which, in addition to having excellent barrier properties against gases, also allows the packaging laminate to be sealed by so-called induction sealing, which is a rapid, simple and effective heat-sealing technique.
- Examples of usable polymers for the liquid-tight, heat-sealable
outer layers web 208 in the method according to the invention are polyolefins, such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and polypropylene (PP). - From a web of the packaging laminate 10 in
Figure 1 for example, it is possible, to produce dimensionally stable packaging containers of a disposable type for oxygen-sensitive liquid foods, such as milk, juice, wine and cooking oil, by folding and heat-sealing in a manner known per se. Such packaging containers are nowadays produced with the aid of modern packaging machines of the type in which finished packages are shaped, filled and sealed. - One way in which packaging containers made of the packaging laminate 10 in
Figure 1 can be shaped, filled and sealed is illustrated inFigure 3 . The so-called single-use packages are produced from a web by being shaped into atube 31, in which the longitudinal edges 32, 32' of the web are joined to each other in anoverlap seam 33 by melting together the mutually facing surfaces of theplastic layers packaging units 36 by repeated pressing-together and heat-sealing of the tube transversely with respect to thelongitudinal direction 35 of the tube, below the product level of the tube, and the packaging units are separated from each other and finally given the desired geometric shape, usually a parallelepipedal shape like a brick, by means of at least one further folding and heat-sealing step. - A well-known example of a single-use package of this type is the commercial package sold under the name Tetra Brik aseptic, which is shown in
Figure 4 . In addition to the characteristic brick-like outer shape, a unique feature of this commercial type of packaging is that it is produced more or less completely by folding and heat-sealing 41, 42 of the web-shaped packaging laminate, without the use of extra packaging parts such as separate tops and/or bottoms.Such packaging containers 40 can also be provided with asuitable opening arrangement 43, for example a screw cap which, when opened, penetrates and removes the packaging material and permits emptying of the packaged product. For this purpose, the laminated packaging laminate can have perforations in the paperboard layer that has been laminated in between the polymers and barrier layers of the laminate. Alternatively, a hole is punched in the laminated packaging material immediately before the filling process, after which the hole is provided with a tape or pull-tab, on both sides of the packaging material. After the packaging container has been filled and sealed, an opening arrangement in the form of a hinge or screw cap can be applied on top of the covered hole. Alternatively, an opening arrangement is applied which is cast onto a punched hole directly during the filling process. It is not necessary to provide the packaging container with an opening device, it can also be torn open by means of a tear-perforation, or by cutting. - Alternatively, packaging containers can be produced as above but have, as their final shape, the pillow shape that is obtained directly after the packaging units have been separated from each other and that is not therefore further shaped by folding. Such a package is generally produced using a thinner paperboard material and therefore entails greater demands on adhesion and integrity of the packaging material with regard to the lamination layers and also to the mechanical strength characteristics, in particular the elastic characteristics, of the polymer layers. An example of one such package is shown in
Figure 5 . - Packaging containers for oxygen-sensitive liquid food, for example juice, can also be produced from sheet-like blanks or prefabricated blanks of the packaging laminate 10 in
Figure 1 . From a tubular blank of the packaging laminate 10 that is folded flat, packages are produced by first of all building the blank up to form an open tubular container capsule, of which one open end is closed off by means of folding and heat-sealing of integral end panels. The thus closed container capsule is filled with the food product in question, e.g. juice, through its open end, which is thereafter closed off by means of further folding and heat-sealing of corresponding integral end panels. An example of a packaging container produced from sheet-like and tubular blanks is shown inFigure 6 and is a so-called gable-top package 60. There are also packages of this type which have a moulded top and/or screw cap made of plastic. - Packaging laminate 10 was produced with the composition indicated in the following table:
Laminate layer Reference sign in figures Coating quantity, g/m2 (reference example 1) Coating quantity, g/m2 (Comparative Example 1) Low-density polyethylene (LDPE) 14 12 12 Paperboard 11 Ethylene-acrylic acid copolymer (EAA) 13b --- 3 (Primacor 3540 Dow; with about 3,2 mol-% carboxylic acid groups) Low-density polyethylene (LDPE) 13a 20 10 (Novex 19N730) (Novex 19N730) (Autoclave-LDPE) Ethylene-acrylic acid copolymer (EAA) 13c --- 3 (Primacor 3540 Dow) Aluminium foil 12 6.3 µm 6.3 µm Ethylene-acrylic acid copolymer (EAA) (not shown) 6 6 Blend of LDPE and m-LLDPE (weight ratio 30:70) 15 19 19 - Packaging laminate 10 was produced by co-extrusion of the material layers 13a-13c as a three-layer structure, with the material layers included in the
sequence 13b/13a/13c. This co-extrusion could generally be carried out at an extrusion speed of 200 m/min and at an extrusion temperature of below 310 °C and without the use of ozone or other extra chemicals to achieve and maintain a permanent binding of thealuminium foil 12, serving as gas barrier, to the paper orpaperboard layer 11 of the packaging laminate. The paperboard material used throughout was CLC/C material with a flexural stiffness of 260 mN. The three layers were able to be co-extruded at the temperatures 290 -310 - 290 °C and at a web speed of 650 m/min, with excellent (non-measurable, above the detection limit) adhesion to the paperboard layer or barrier layer. - The known packaging laminate of the prior art, constituting a further reference example 1, was produced in a similar manner by extrusion of only the
material layer 13a, of LDPE only, but in this case an extrusion temperature as high as 325 °C was needed, together with addition of ozone, to achieve an acceptable binding between thealuminium foil 12 and the paper orpaperboard layer 11. A packaging laminate produced by the method according to Comparative Example 1 thus has considerable environmental and health-related advantages over a corresponding packaging laminate produced in the known way, i.e. without use of adhesive chemicals in direct contact with the paper or paperboard layer and with the layer serving as gas barrier, in this case the aluminium foil. The adhesion obtained, in the example according to Comparative Example 1, between the laminating material and the aluminium foil was improved to such an extent that the layers could no longer be separated along the interfaces between these two materials, i.e. the adherence was higher than the detection limit in the peel test, which is about 200 N/m. By way of comparison, satisfactory adhesion between the laminating material and the aluminium foil was also obtained in the reference example, by means of a higher extrusion temperature and also surface treatment with ozone, but the adhesion was not so great that the layers could not be separated (mean value 105 N/m). After shaping into packaging containers, satisfactory packaging integrity was obtained, i.e. durability and tightness both to liquid and oxygen, with the packaging laminates from both Comparative Example 1 and the reference example. - In a peel test, strips of packaging laminate measuring 15 mm in width are cut, and the two layers between which the adherence is to be measured are separated/delaminated. The two flaps of the delaminated strips are clamped in a tension testing machine, where the strips are further delaminated under controlled conditions at a delamination angle of 90°. The force during the delamination is measured with a load cell, and the peel test value is indicated by the unit N/m. The method is a variation of ASTM D903 - 98 (2010) "Standard Test Method for Peel or Stripping Strength of Adhesive Bonds", with the difference that the specimen width is 15 mm instead of 25 mm and the delamination angle is 90° instead of 180°.
- Moreover, with the purpose of testing the ability of the packaging laminate to withstand impact or percussion, like when a packaging container falls down on the floor from a certain height, observations made by an internal test method surprisingly showed a significant improvement, up to more than 30 %, of the durability of the packaging laminate of Comparative Example 1 compared to the packaging laminate of the reference example 1.
- Comparative Example 1 was repeated with the difference that Primacor™ 3460 (having about 3,6-4,0 mol-% of carboxlic acid groups) was used as adhesive polymer in both
outer layers - In both Comparative Examples 1 and 2, there was gel formation occurring at difficult circumstances in the heated melting and extrusion equipment, due to degradation induced by the carboxylic acid groups of the adhesive polymers. By optimising the extrusion lamination conditions, this is possible to prevent to a sufficient extent by thorough surveillance of the extrusion process. The window of operation, within which a good lamination result may be obtained is however narrow, and needs careful attention by operators and control systems. Lowering the extrusion temperature further in order to avoid gel formation, was found not to be an option. At 280 °C there was no, or insufficient adhesion of the adhesive polymer layer to the paperboard (no fibre tear).
- Comparative Example 1 was repeated with the difference that Novex M21N (having a carboxylic acid group (methacrylic acid) content of about 0,4 mol-%) was used as adhesive polymer in both
outer layers - Comparative Example 1 was repeated with the difference that Novex M21N (having a carboxylic acid group (methacrylic acid) content of about 0,4 mol-%) was used as adhesive polymer in both
outer layers - The results from Example 4 were very positive, regarding adhesion to paperboard as well as to aluminium foil and regarding gel formation. Improved adhesion to the aluminium foil (above 200 N/m, i.e. inseparable, as in Comparative Example 1) was seen, and in particular the adhesion result to the paperboard was improved. There was no separation between the paperboard layer and the adhesive polymer layer, but tear within the fibrous paperboard layer, so-called "Fibre-tear". There was no trace of gel formation observed, neither in the adhesive layers nor in the extrusion equipment under the same conditions as in Example 3.
- Thus, when lowering the amount of carboxylic acid monomer unit content in the adhesive polymer, it was surprisingly found that improved and more robust adhesion results were obtained, and in particular that the operating window could be widened such that higher extrusion temperatures in the adhesive polymer layers may be used, without risk for gel formation and particles in the adhesive polymer layer or in the extrusion equipment. Still, high extrusion temperatures as needed when extruding LDPE alone (Example 2) are not needed for achieving good adhesion.
- Accordingly, the use of an adhesive ethylene co-polymer having a lower carboxylic acid content, makes it possible to manufacture improved packaging laminates, without gel particles in the adhesive polymer applied, but still with excellent adhesion between the laminating material and the paperboard surface, and without need for surface treatments such as ozone treatment. Similar packaging laminates having a higher acid content in the laminating material will either have too low adhesion to paperboard, or a high risk for gel degradation particles present in the adhesive layers. At continuous and industrial production of packaging laminates, this is an evident and notable improvement.
Claims (14)
- Packaging laminate for a packaging container for oxygen-sensitive liquid food, which packaging laminate comprises a layer (11) of paper or paperboard, and a material layer (12) of aluminium serving as a gas or vapour barrier layer, which layers (11 and 12) are bonded to each other by a laminating material (13), comprising a central polymer layer (13a) which, on one surface, has a first adhesive layer (13b) of a first adhesive polymer composition with the ability to bind to the paper or paperboard layer (11) and, on its other surface, has a second adhesive layer (13c) of a second adhesive polymer composition with the ability to bind to the material layer (12) serving as gas barrier, wherein the first adhesive layer (13b) on one surface of the central polymer layer (13a) is in contact with the paper or paperboard layer (11), and wherein the second adhesive layer (13c) on the other surface of the central polymer layer (13a) is in contact with the layer (12) of aluminium serving as gas or vapour barrier, the first adhesive polymer composition comprising ethylene monomer units and from 0,15 to below 1,5 mol%, of monomer units having carboxylic acid functional groups, of the total first adhesive polymer composition, and the second adhesive polymer layer (13c) having the same adhesive polymer composition as the first adhesive layer (13b).
- Packaging laminate according to claim 1, wherein the first adhesive polymer composition comprises ethylene monomer units and from 0,15 to 1,3 mol%, more preferably from 0,15 to 0,7 mol%, most preferably from 0,15 to 0,4 mol%, of monomer units having carboxylic acid functional groups, of the total first adhesive polymer composition.
- Packaging laminate according to any one of Claims 1-2, wherein the first adhesive polymer composition comprises a low density polyethylene (LDPE) at an amount of up to 60 wt-%.
- Packaging laminate according to any one of the preceding Claims, wherein the first adhesive polymer or polymer composition comprises an adhesive polymer selected from the group consisting of ethylene-acrylic acid copolymer (EAA) and ethylene-methacrylic acid copolymer (EMAA) and blends thereof.
- Packaging laminate according to any one of the preceding Claims, further having a heat sealable food product contact layer (15) comprising a polyethylene selected from the group consisting of LDPE, linear low density polyethylene (LLDPE) and linear low density polyethylene polymerised by a single site catalyst (m-LLDPE), and blends of two or more thereof.
- Packaging laminate according to any one of the preceding Claims, wherein the central layer of the laminating material (13a) has a thickness of from 10 to 14 g/m2, and the first and second adhesive polymer layers (13b, 13c) of the laminating material each have a thickness of from 2 to 5 g/m2, such as from 3 to 4 g/m2.
- Packaging laminate according to any one of the preceding Claims, wherein the material layer serving as a barrier layer (12), on its opposite side, which is to form the inside of the packaging laminate in a packaging container, is bonded to a heat sealable food product contact layer (15) of polyethylene by an inside adhesive polymer layer (16), which is in direct contact with the barrier layer (12), the inside adhesive polymer layer consisting of a polymer having ethylene monomer units and monomer units having carboxylic acid functional groups, which amount to from 1,5 mol% and above, preferably from 1,5 mol% to 3,5 mol%, more preferably from 1,5 mol% to 3,3 mol%, of the inside adhesive polymer.
- Packaging laminate according to any one of the preceding Claims, wherein the central polymer layer (13a) comprises a polyolefin, such as a polyethylene.
- Packaging laminate according to any one of the preceding Claims, wherein the central polymer layer (13a) comprises a polyethylene chosen from a group consisting of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylenes (VLDPE), ultra low-density polyethylenes (ULDPE), linear low-density polyethylene which has been produced with a so-called single-site catalyst, metallocene catalyst or so-called constrained-geometry catalyst (m-LLDPE), medium-density polyethylene (MDPE) and high-density polyethylene (HDPE).
- Packaging laminate according to any one of the preceding Claims, wherein the adhesion between the first adhesive composition and the paper or paperboard is so high that it generates fibre tear within the paper or paperboard layer, upon adhesion testing according to ASTMD903-98(2010).
- Packaging laminate according to any one of the preceding Claims, wherein the adhesion between the aluminium barrier layer and the laminating material (13) is higher than 105 N/m, such as higher than 200 N/m.
- Packaging container for oxygen-sensitive liquid food, e.g. milk, juice, wine, cooking oil, etc., produced from the packaging laminate (10) according to any of Claims 1-11.
- Method of producing the packaging laminate according to any one of claims 1-11, wherein the layer (11) of paper or paperboard is laminated to the material layer (12) of aluminium serving as a gas or vapour barrier layer, by melt (co-)extrusion lamination with the laminating material (13b,13a,13c).
- Method according to claim 13, wherein the melt co-extrusion lamination is done without any surface treatment, such as ozone treatment.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE1450945 | 2014-08-14 | ||
PCT/EP2015/068690 WO2016023993A1 (en) | 2014-08-14 | 2015-08-13 | Packaging laminate, method for producing same, and packaging container produced from the packaging laminate |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3194164A1 EP3194164A1 (en) | 2017-07-26 |
EP3194164B1 true EP3194164B1 (en) | 2020-04-08 |
Family
ID=54012168
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15756580.5A Active EP3194164B1 (en) | 2014-08-14 | 2015-08-13 | Packaging laminate, method for producing same, and packaging container produced from the packaging laminate |
Country Status (6)
Country | Link |
---|---|
US (1) | US20170225439A1 (en) |
EP (1) | EP3194164B1 (en) |
JP (1) | JP6737772B2 (en) |
CN (1) | CN106660315B (en) |
RU (1) | RU2693757C2 (en) |
WO (1) | WO2016023993A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021164913A1 (en) | 2020-02-18 | 2021-08-26 | Constantia Pirk Gmbh & Co. Kg | Recyclable paper packaging with high barrier to water vapor and oxygen |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2667625T3 (en) | 2013-12-19 | 2018-05-11 | Borealis Ag | Low density polyethylene extrusion coating and heat sealed article made from it |
WO2018081533A1 (en) * | 2016-10-28 | 2018-05-03 | Selig Sealing Products, Inc. | Sealing member for use with fat containing compositions |
US20190084745A1 (en) * | 2017-09-19 | 2019-03-21 | Cameron Ernest Jabara | Disposable beverage container and method of operation |
EP3700750A4 (en) * | 2017-10-26 | 2021-05-26 | AdvanSix Resins & Chemicals LLC | Multilayer package structure for ozone scavenging |
JP7101050B2 (en) * | 2018-06-07 | 2022-07-14 | 関西チューブ株式会社 | A raw fabric for a light-shielding laminated tube, a body portion using the raw fabric, a container, and a method for manufacturing the body portion. |
CN109895467B (en) * | 2019-01-31 | 2020-05-22 | 威海恒瑞新型包装材料有限公司 | Antibacterial self-adhesive laminating paper |
EP4149756A1 (en) | 2020-05-11 | 2023-03-22 | Cryovac, LLC | Multilayer film having a soluble tie layer and method for dissipating |
BR202022008632U2 (en) * | 2022-05-04 | 2023-11-14 | João Marques Fernandes | CONSTRUCTIVE ARRANGEMENT FOR OPENING CARTON PACKAGING |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4599392A (en) * | 1983-06-13 | 1986-07-08 | The Dow Chemical Company | Interpolymers of ethylene and unsaturated carboxylic acids |
JP2000037831A (en) * | 1998-07-24 | 2000-02-08 | Nippon Polyolefin Kk | Gas barrier paper container |
EP1118459A4 (en) * | 1998-07-24 | 2008-03-12 | Japan Polyolefins Co Ltd | Gas barrier laminate, process for producing the same, and paper container made using the laminate |
US6437046B1 (en) * | 2000-10-04 | 2002-08-20 | E. I. Du Pont De Nemours And Company | Low-acid ethylene copolymers for improving the adhesion of LDPE to aluminum foil in extrusion coating |
US7235306B2 (en) * | 2002-11-22 | 2007-06-26 | Brpp, Llc | Flavor barrier |
BRPI0415579A (en) * | 2003-10-17 | 2007-01-02 | Du Pont | multilayer structure, packaging and process |
SE528259C2 (en) * | 2004-12-22 | 2006-10-03 | Tetra Laval Holdings & Finance | Packaging laminates, methods in connection with their manufacture, film for its manufacture and a packaging container |
CN101233184B (en) * | 2005-05-31 | 2012-12-26 | 三井·杜邦聚合化学株式会社 | Resin composition, and film, sheet or laminate formed from the same |
US20100120313A1 (en) * | 2005-06-29 | 2010-05-13 | Bohme Reinhard D | Packaging Material |
US7951873B2 (en) * | 2006-05-05 | 2011-05-31 | Exxonmobil Chemical Patents Inc. | Linear low density polymer blends and articles made therefrom |
US8201712B2 (en) * | 2008-02-06 | 2012-06-19 | The Coca-Cola Company | Carton-based packaging for a beverage dispenser |
JP5649812B2 (en) * | 2008-11-20 | 2015-01-07 | 日本ポリプロ株式会社 | A novel triarylphosphine or triarylarsine compound, an α-olefin polymerization catalyst using them, and a method for producing an α-olefin copolymer. |
JP5661239B2 (en) * | 2008-12-10 | 2015-01-28 | 大日本印刷株式会社 | Liquid paper container |
CN104334459B (en) * | 2012-08-10 | 2018-02-02 | 日本制纸株式会社 | Multi-ply paper container |
SE538048C2 (en) * | 2012-11-30 | 2016-02-23 | Stora Enso Oyj | Process for making a packaging material |
EP2767397A1 (en) * | 2013-02-18 | 2014-08-20 | Tetra Laval Holdings & Finance S.A. | Packaging laminate, method for producing same, and packaging container produced from the packaging container |
-
2015
- 2015-08-13 CN CN201580043617.4A patent/CN106660315B/en active Active
- 2015-08-13 US US15/502,855 patent/US20170225439A1/en not_active Abandoned
- 2015-08-13 WO PCT/EP2015/068690 patent/WO2016023993A1/en active Application Filing
- 2015-08-13 RU RU2017107960A patent/RU2693757C2/en active
- 2015-08-13 JP JP2017508023A patent/JP6737772B2/en active Active
- 2015-08-13 EP EP15756580.5A patent/EP3194164B1/en active Active
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021164913A1 (en) | 2020-02-18 | 2021-08-26 | Constantia Pirk Gmbh & Co. Kg | Recyclable paper packaging with high barrier to water vapor and oxygen |
EP4169707A1 (en) | 2020-02-18 | 2023-04-26 | Constantia Pirk GmbH & Co. KG | Recyclable paper package with high barrier against water vapour and oxygen |
Also Published As
Publication number | Publication date |
---|---|
JP6737772B2 (en) | 2020-08-12 |
RU2017107960A3 (en) | 2019-01-24 |
RU2693757C2 (en) | 2019-07-04 |
CN106660315B (en) | 2019-07-12 |
RU2017107960A (en) | 2018-09-14 |
CN106660315A (en) | 2017-05-10 |
JP2017524620A (en) | 2017-08-31 |
US20170225439A1 (en) | 2017-08-10 |
WO2016023993A1 (en) | 2016-02-18 |
EP3194164A1 (en) | 2017-07-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3194164B1 (en) | Packaging laminate, method for producing same, and packaging container produced from the packaging laminate | |
EP2956303B2 (en) | Packaging laminate, method for producing same, and packaging container produced from the packaging laminate | |
US7935400B2 (en) | Packaging laminate, method for its manufacturing and packaging container manufactured from the packaging laminate | |
EP2475520B1 (en) | A barrier coated thermo-mechanically stable, heat sealable film, a packaging laminate comprising the film, a packaging container formed from the packaging laminate and a method for the production of the film | |
EP1791761A1 (en) | A strip tape, a packaging container having such a strip tape, and a method of producing such a strip tape | |
US6949275B2 (en) | Packaging laminate and container including it | |
CN110678326B (en) | Laminated packaging material and opening film material, packaging container made therefrom and method for making laminated material | |
EP3368300B1 (en) | Laminated packaging material comprising a barrier film and packaging containers manufactured therefrom | |
EP4371755A1 (en) | Laminated packaging material, method for manufacturing it and packaging containers comprising it | |
EP4253047A1 (en) | A laminated packaging material and packaging container manufactured therefrom | |
EP4371754A1 (en) | Laminated packaging material, method for manufacturing it and packaging containers comprising it | |
EP3368302B1 (en) | Laminated packaging material comprising a barrier film and packaging containers manufactured therefrom | |
AU2023245512A1 (en) | A laminated packaging material and packaging container manufactured therefrom | |
JP2004224343A (en) | Strip tape and packaging container | |
JP2009280264A (en) | Strip for packaging container, method of manufacturing the strip for packaging container and packaging container |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170314 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B32B 15/085 20060101AFI20191010BHEP Ipc: B32B 27/10 20060101ALI20191010BHEP Ipc: B32B 27/30 20060101ALI20191010BHEP Ipc: B65D 5/00 20060101ALI20191010BHEP Ipc: B32B 27/08 20060101ALI20191010BHEP Ipc: B32B 7/12 20060101ALI20191010BHEP Ipc: B32B 27/32 20060101ALI20191010BHEP Ipc: B32B 29/00 20060101ALI20191010BHEP Ipc: B65D 77/00 20060101ALI20191010BHEP Ipc: B32B 15/20 20060101ALI20191010BHEP |
|
INTG | Intention to grant announced |
Effective date: 20191028 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 1253816 Country of ref document: AT Kind code of ref document: T Effective date: 20200415 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602015050329 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20200408 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200709 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200708 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200817 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200808 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1253816 Country of ref document: AT Kind code of ref document: T Effective date: 20200408 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200708 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602015050329 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 |
|
26N | No opposition filed |
Effective date: 20210112 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200813 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200813 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200813 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200813 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200408 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230426 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230822 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230828 Year of fee payment: 9 |